EP2881439B1 - Polyamide compositions - Google Patents

Polyamide compositions Download PDF

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Publication number
EP2881439B1
EP2881439B1 EP14194508.9A EP14194508A EP2881439B1 EP 2881439 B1 EP2881439 B1 EP 2881439B1 EP 14194508 A EP14194508 A EP 14194508A EP 2881439 B1 EP2881439 B1 EP 2881439B1
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Prior art keywords
weight
range
moulding compositions
compositions according
copolymer
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EP14194508.9A
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German (de)
French (fr)
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EP2881439A1 (en
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Tobias Benighaus
Detlev Joachimi
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Priority to PL14194508T priority Critical patent/PL2881439T3/en
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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    • C08K5/00—Use of organic ingredients
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    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/025—Copolymer of an unspecified olefin with a monomer other than an olefin
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Definitions

  • the present invention relates to thermoplastic molding compositions based on at least one polyamide containing at least one polyol and at least one copolymer of at least one olefin with at least one methacrylic acid ester or acrylic ester of an aliphatic alcohol. Furthermore, this invention relates to products, in particular fibers, films and moldings from these molding compositions and their use. In addition, this invention relates to the use of the claimed copolymers to reduce the deposit formation of polyamide molding compositions or on the products obtainable from these molding compositions containing at least one polyol of the series pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Polyamides are often used as materials for moldings that are exposed to elevated temperatures over a longer period during their lifetime. For a variety of applications, it is necessary that the materials be sufficiently stable to the thermo-oxidative damage that may occur during the lifetime of a product made from these materials, particularly when such products are used in the engine compartment of motor vehicles. Polyamides generally show a deterioration in their mechanical properties when exposed to elevated temperatures for extended periods of time. This effect is based primarily on the oxidative damage of the polymer at elevated temperatures (thermo-oxidative damage). A longer period in the sense of the present invention means longer than 100 hours, elevated temperatures in the sense of the present invention means higher than 80 ° C.
  • thermoplastic molding compositions to thermo-oxidative damage is usually assessed by comparing mechanical properties, in particular by comparing the tensile stress at break and elongation at break at a defined temperature measured in the tensile test according to ISO 527 over a defined period of time.
  • Numerous systems for stabilizing polymers against thermo-oxidative damage and the resulting molecular degradation are known and have been described in the literature. A summary can be found in the " Plastic Additives Handbook ", 5th Edition, publisher: Hans Zweifel, Carl Hanser Verlag, Kunststoff 2001 , pages 10 to 19 and 40 to 92.
  • thermoplastics especially polyamides
  • antioxidants based on sterically hindered phenols or based on aromatic amines used as organic stabilizers or systems based on copper compounds as inorganic stabilizers.
  • the said organic stabilizers are generally used at temperatures up to about 120 ° C, some are still effective at higher temperatures.
  • An effective stabilization at higher temperatures up to about 140 ° C is usually achieved by stabilizer systems based on mixtures of copper halides and alkali halides.
  • WO2010 / 014785 A1 describes polyamide molding compositions which are stabilized by the addition of polyols, especially dipentaerythritol and tripentaerythritol, for temperatures up to 230 ° C.
  • WO2011 / 014556 A1 teaches that also polyamide molding compositions based on mixtures of partially aromatic polyamides and amorphous polyamides can be stabilized with these polyols.
  • CN102030982 A describes a stabilizer system for polyamide molding compounds, which consists of an elemental metal and polyols, in particular dipentaerythritol.
  • short-chain polyols are usually also used to improve the flowability of polyamide-based molding compositions.
  • EP 1041109 A2 Polyamide-based molding compositions whose flowability is significantly improved by the addition of polyols, especially of pentaerythritol and dipentaerythritol, without significantly deteriorating the mechanical properties of the molding compositions.
  • thermoplastic articles based on, for example, polyamide (6T / DT), a polyol, glass fibers and other additives which are stable to thermo-oxidative damage.
  • WO2007 / 036929 A1 describes a process for the production of polyamide resins with improved flowability, in which polyol, especially pentaerythritol, is added to the polyamide during the polymerization.
  • polyamide-based molding compositions containing polyols have the disadvantage that the polyols partially migrate to the surface under humid climatic conditions.
  • Humid climatic conditions for the purposes of this invention are when the temperature is higher than 25 ° C and the relative humidity higher than 65%. This migration leads to the formation of coatings on the surfaces of moldings, fibers or films, which are made from such polyamide molding compounds. Such surface coverings disturb the aesthetic sensibility of the customer and can also significantly reduce the adhesion of adhesives or sealants.
  • the object of the present invention was therefore to provide compositions based on polyamide and polyamide-based thermoplastic molding compositions which thus provide improved stability against thermo-oxidative damage and improved flowability, but at the same time form surface coatings to a much lesser extent under humid climatic conditions.
  • the flowability of thermoplastic molding compositions is usually assessed by comparing the melt viscosity or the volume flow index.
  • the melt viscosity is determined in general and also in the context of the present invention in a capillary viscometer according to ISO 11443. Low melt viscosity values indicate good flowability.
  • the shear rate range at about 1000 1 / s to 1500 1 / s is particularly relevant for statements about the flowability in the injection molding process.
  • the volume flow index is determined in general and also in the context of the present invention according to DIN EN ISO 1133-1 at a defined temperature and defined load weight. A high value for the volume flow index indicates a good flowability.
  • copolymers of at least one olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol as flow improver of polyamide-based molding compositions is made WO 2005/121249 A1 known.
  • thermooxidative degradation was in the context of the present invention by the Breaking voltage determined.
  • Breaking force is a term used in materials testing for the force needed to break or tear a specimen.
  • the tensile strength is usually as a force (in N) or - based on the cross-sectional area of the sample - as a breakdown voltage (in N / mm 2) indicated.
  • tensile test or bending test it is defined by the force drop that occurs when the maximum force is exceeded at which the material is still elastically deformed. If the force falls z. By 20%, the universal testing machine detects that the sample has broken.
  • the breaking stress ⁇ B was determined in the context of the present invention according to EN ISO 527-1 (ISO version February 2012) by tensile tests with a tensile testing machine (see also: http://de.wikipedia.org/wiki/Zugpr%C3%BCfmaschine ).
  • the solution of the problem and thus the subject of the present invention is therefore the use of at least one of the abovementioned copolymers to reduce the formation of deposits in the humid climate in thermoplastic molding compositions or products to be produced therefrom containing polyamide and at least one polyol, the polyols having organic molecules at least two and at most 12 hydroxyl groups per molecule and a mean molecular weight in the range of 64 to 2000 g / mol, wherein in the case of the use of polyols which are mixtures of oligomeric and / or polymeric polyols, for this component of the mixture in place of molecular weight is the number average molecular weight (M n ) applies.
  • M n number average molecular weight
  • thermoplastic molding compositions according to the invention in addition to the components (a) to (c) still contain (d) 5 to 80 wt .-% of at least one filler or reinforcing material, preferably glass fibers or carbon fibers, particularly preferably glass fibers, wherein the proportions at least one of the components (a) to (c) are to be reduced such that the sum of all weight percentages always equals 100.
  • filler or reinforcing material preferably glass fibers or carbon fibers, particularly preferably glass fibers
  • inventive thermoplastic molding compositions in addition to the components (a) to (d) or instead of (d) still (e) 0.1 to 20 wt .-% of at least one form of carbon black and / or nigrosine, preferably carbon black, wherein the proportions of at least one of the components (a) to (c) and, if appropriate, (d) are to be reduced so that the sum of all weight percentages always equals 100.
  • the present invention relates to the use of the thermoplastic molding compositions in injection molding, in blow molding or in extrusion for the production of products, in particular fibers, films or moldings, of any kind.
  • the present invention further relates to the use of these products for the manufacture of articles for the electrical, electronics, telecommunications, information technology, solar, computer, household, sports, medical or entertainment industries preferred for motor vehicles, most preferably for the engine compartment of motor vehicles.
  • the polyamides to be used as component (a) may be amorphous polyamides, semicrystalline polyamides or partially crystalline polyamides.
  • the polyamides to be used as component (a) are preferably partially crystalline polyamides, particularly preferably semi-crystalline polyamides having a melting point of at least 180 ° C.
  • the semicrystalline polyamides to be used in one embodiment as component (a) are preferably selected from the group PA6, PA66, PA610, PA612, PA10, PA810, PA106, PA1010, PA11, PA1011, PA1012, PA1210; PA1212, PA814, PA1014, PA618, PA512, PA613, PA813, PA914, PA1015, PA11, PA12 or a partly aromatic polyamide, a so-called polyphthalamide (PPA).
  • PPA polyphthalamide
  • Preferred PPAs are PA66 / 6T, PA6 / 6T, PA6T / MPMDT (MPMD stands for 2-methylpentamethylenediamine), PA9T, PA10T, PA11T, PA12T, PA14T and copolycondensates of these last types with an aliphatic diamine and an aliphatic dicarboxylic acid or with an ⁇ , ⁇ -aminocarboxylic acid or a lactam.
  • Semicrystalline polyamides according to DE 10 2011 084 519 A1 have a melting enthalpy of more than 25 J / g, measured by the DSC method according to ISO11357 during the 2nd heating and integration of the melt peak.
  • Particularly preferred according to the invention is used as the partially crystalline polyamide of component (a) PA6 or PA66 or a copolyamide of PA6 or PA66.
  • the semicrystalline polyamide to be used in one embodiment as component (a) has according to DE 10 2011 084 519 A1 a melting enthalpy in the range of 4 to 25 J / g, measured by the DSC method according to ISO 11357 at the 2nd heating and integration of the melt peak.
  • Preferred semicrystalline polyamides are those which are prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
  • Suitable starting materials are aliphatic and / or aromatic dicarboxylic acids, more preferably adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or aromatic diamines, particularly preferably tetramethylenediamine, Hexamethylenediamine, 2-methylpentane-1,5-diamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomers diamino-dicyclohexylmethane, diaminodicyclohexylpropane, bis-aminomethyl-cyclohexane, phenylenediamine, xylylenediamine , Aminocarbon Acid, in particular aminocaproic acid, or the corresponding lactams into consideration.
  • a blend of different polyamides is used as component (a).
  • Most particularly preferred are most PA6, PA66 and other based on aliphatic or / and aromatic polyamides or copolyamides compounds in which come to a polyamide group in the polymer chain 3 to 11 methylene groups.
  • the used in the present application marking the polyamides corresponds to international standard, wherein the first digit (s) indicate the C atomic number of Trustdiamins and the last digit (s) the C atomic number of the dicarboxylic acid. If only one number is given, as in the case of PA6, this means that an ⁇ , ⁇ -aminocarboxylic acid or the lactam derived therefrom, in the case of PA6, ie ⁇ -caprolactam, has been used as starting material; Incidentally, reference is made to H. Domininghaus, The Plastics and their properties, pages 272 et seq., VDI-Verlag, 1976.
  • component (a) at least one partially crystalline polyamide having a viscosity number determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307 in the range of 80 to 180 ml / g , more preferably used in the range of 90 to 160 ml / g.
  • the amorphous polyamides to be used in one embodiment have according to DE 10 2011 084 519 A1 a melting enthalpy of less than 4 J / g, measured by the DSC method according to ISO 11357 at the 2nd heating and integration of the melting peak.
  • amorphous polyamides are in the DE 10 2008 046 682 A1 described, in turn GB-PS 619 707 .
  • DE-OS 15 95 354 .
  • DE-PS 26 42 244 and US-PS 42 93 687 refers whose contents reveal exemplary amorphous polyamides in the context of the present invention.
  • the polyamides to be used in the thermoplastic molding compositions according to the invention can be prepared by various processes and synthesized from different building blocks. For the preparation of polyamides, a variety of procedures are known, depending on the desired end product different monomer units and, different chain regulators for setting a desired molecular weight, or different monomers with corresponding reactive groups for later intended aftertreatments are used.
  • the polyols to be used according to the invention as component (b) are also known under the names "polyalcohol” or "polyhydric alcohol”.
  • the at least one polyol to be used according to the invention as component (b) comprises organic molecules having at least 2 and at most 12 hydroxyl groups per molecule, the average molecular weight of the polyol or polyols being in the range from 64 to 2000 g / mol. Preference is given to using polyols having at least 3 and at most 10 hydroxyl groups per molecule, more preferably having at least 4 and not more than 8 hydroxyl groups per molecule.
  • the number average molecular weight (M n ) is used instead of the molecular weight for this component of the mixture for the determination of the limits of the claimed range.
  • the at least one polyol to be used as component (b) preferably has an aliphatic or aromatic structure or a combination of these two features.
  • the aliphatic chains within a polyol to be used according to the invention as component (b) contain not only carbon atoms but also heteroatoms, preferably nitrogen, oxygen or sulfur.
  • the polyols to be used according to the invention also have, in addition to the hydroxyl groups, further functional groups, preferably ether groups, carboxylic acid groups, amide groups or ester groups.
  • Particularly preferred as component (b) polyols having more than two hydroxyl groups are those polyols having three hydroxyl groups of the group glycerol, trimethylolpropane, 2,3-di (2'-hydroxyethyl) cyclohexan-1-ol, hexane-1,2 , 6-triol, 1,1,1-tris (hydroxymethyl) ethane, 3- (2'-hydroxyethoxy) -propane-1,2-diol, 3- (2'-hydroxypropoxy) -propane-1,2- diol, 2- (2'-hydroxyethoxy) -hexane-1,2-diol, 6- (2'-hydroxypropoxy) -hexane-1,2-diol, 1,1,1-tris - [(2
  • Polyols of the series D-mannitol, D-sorbitol, dulcitol, arabitol, inositol, xylitol, talitol, allitol, altritol, adonite, erythritol, threitol, pentaerythritol, dipentaerythritol and others which are particularly preferred as component (b) are polyols Tripentaerythritol, and polyols from the group of monosaccharides, especially mannose, glucose, galactose, fructose, D-xylose, arabinose, D-idose, D-erythrose, D-threose, D-ribose, D-lyxose, D-allose, D -Altrose, D-gulose, D-talose, D-ribulose, D-erythrulose, D-xylulose, D-psico
  • component (b) polyols to be used are those having more than three hydroxyl groups.
  • Very particular preference is given to using at least one polyol of the series pentaerythritol, dipentaerythritol, tripentaerythritol and di-trimethylolpropane, particular preference being given to pentaerythritol, dipentaerythritol and tripentaerythritol, in particular very particular preference to dipentaerythritol.
  • the novel thermoplastic molding compositions comprise at least one copolymer, preferably at least one random copolymer of at least one olefin, preferably ⁇ -olefin, and at least one methacrylic acid ester or acrylic ester of an aliphatic alcohol, which measures a melt flow index (MFI) at 190 ° C and a load of 2.16 kg of at least 100 g / 10 min.
  • MFI melt flow index
  • the copolymer to be used as component (c) consists of less than 4% by weight, more preferably less than 1.5% by weight and most preferably 0% by weight of monomer building blocks which are further reactive functional groups selected from the group comprising epoxides, oxetanes, anhydrides, imides, aziridines, furans, acids, amines, oxazolines.
  • Suitable olefins preferably ⁇ -olefins as constituent of the copolymers to be used as component (c), preferably have between 2 and 10 carbon atoms and may be unsubstituted or substituted by one or more aliphatic, cycloaliphatic or aromatic groups.
  • Preferred olefins are selected from the group comprising ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene.
  • Particularly preferred olefins are ethene and propene, most preferably ethene.
  • the further reactive functional groups of the copolymer (c) are introduced exclusively via the olefins into the copolymer (c), these functional groups being selected from the group comprising epoxides, oxetanes, anhydrides, imides, aziridines, furans, Acids, amines, oxazolines.
  • the content of the olefin in the copolymer (c) is in the range of 50 to 90% by weight, preferably in the range of 55 to 75% by weight.
  • the copolymer (c) is further defined by the second component besides the olefin.
  • the second component alkyl esters of acrylic acid or methacrylic acid whose alkyl group is formed of 5-30 carbon atoms are suitable.
  • the alkyl group may be linear or branched and may contain cycloaliphatic groups, but may also be substituted by one or more ether or thioether functions.
  • Suitable methacrylic esters or acrylates in this context are also those synthesized from an alcohol component based on oligoethylene glycol or oligopropylene glycol having only one hydroxyl group and at most 30 carbon atoms.
  • the alkyl group of the methacrylic acid ester or of the acrylic acid ester is preferably selected from the group comprising 1-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 1-heptyl, 3-heptyl, 1-octyl, 1- (2-ethyl) - hexyl, 1-nonyl, 1-decyl, 1-dodecyl, 1-lauryl or 1-octadecyl.
  • Particularly preferred are in particular also branched alkyl groups, which lead to a lower glass transition temperature TG compared to linear alkyl groups of the same number of carbon atoms.
  • copolymers which are to be used as component (c) and are based on ethene and alkyl acrylates whose alkyl group is formed from 5-10 carbon atoms.
  • the further reactive functional groups of the copolymer (c) are introduced exclusively via the acrylic acid esters or methacrylic acid esters into the copolymer to be used as component (c), wherein the functional groups are selected from the group comprising epoxides, oxetanes, anhydrides, imides , Aziridines, furans, acids, amines, oxazolines.
  • the content of the acrylic acid esters or methacrylic acid esters in the copolymer to be used as component (c) is in the range from 10 to 50% by weight, preferably in the range from 25 to 45% by weight.
  • Copolymers to be used as component (c) are distinguished, in addition to the composition, by the low molecular weight. Accordingly, for the compositions according to the invention and the molding compositions obtainable therefrom, only copolymers suitable as component (c) having a melt flow index (MFI) measured at 190 ° C. and a load of 2.16 kg in the range of 100 g / 10 are suitable min to 800 g / 10 min, preferably in the range of 150 g / 10 min to 800 g / 10 min, more preferably in the range of 300 g / 10 min to 700 g / 10 min.
  • MFI melt flow index
  • Copolymers suitable as component (c) can be selected from the group of materials offered by Arkema under the brand name Lotryl® EH, which are usually used as hotmelt adhesives. Particularly preferred according to the invention is a copolymer of ethene and ethylhexyl acrylate (EHA), which is known as Lotryl® 37 EH 550 [ CAS-No. 26984-27-0 ] by Arkema, Puteaux, France.
  • EHA ethene and ethylhexyl acrylate
  • Fillers and reinforcing agents as component (d) for the purposes of the present invention are fibrous, needle-shaped or particulate fillers and reinforcing agents.
  • the fibrous or particulate reinforcing materials are provided in a preferred embodiment for better compatibility with the polyamide to be used as component (a) with suitable surface modifications, in particular surface modifications containing silane compounds.
  • cut glass fibers having an average starting length in the range from 1 to 50 mm, particularly preferably in the range from 1 to 10 mm, very particularly preferably in the range from 2 to 7 mm, are used for component (d).
  • the glass fibers of component (d) may have a smaller d97 or d50 value than the glass fibers originally used due to the processing to the molding compound or to the product in the molding compound or in the product.
  • the arithmetic mean of the glass fiber length after processing is often only in the range of 150 microns to 300 microns.
  • the median value or d50 value is the most important parameter as a measure of the mean particle size. 50% by volume of the sample is finer and the other 50% are coarser than d50.
  • the glass fibers preferably to be used according to the invention as component (d) CAS No. 65997-17-3 ] preferably have an average fiber diameter in the range from 7 to 18 ⁇ m, particularly preferably in the range from 9 to 15 ⁇ m, which can be determined by at least one option available to the person skilled in the art.
  • the glass fibers to be used as component (d) are preferably added as cut or as continuous fibers or ground glass fibers.
  • a determination of the length and diameter / thickness of the individual fiber takes place semi-automatically in the context of the present invention on the basis of scanning electron microscopic images (SEM) by means of a graphics tablet and computer-aided data acquisition.
  • the fibers preferably used as component (d), in particular glass fibers, are preferably provided with a suitable sizing system or an adhesion promoter or adhesion promoter system, particularly preferably with a silane-based adhesion promoter.
  • adhesion promoters are silane compounds from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X in formula (I).
  • the sizing compounds preferably containing silane compounds as adhesion promoter are preferably used in amounts ranging from 0.05 to 2% by weight, more preferably in the range from 0.25 to 1.5% by weight .-% and in particular in the range of 0.5 to 1 wt .-% (wt .-% after drying) based on the glass fibers used for surface coating.
  • the proportion by weight of adhesion promoters, in particular silanes, in the surface coating of the glass fibers is preferably from 2 to 10% by weight of the dry matter.
  • At least one form of carbon black and / or nigrosine, in particular carbon black is used as component (e).
  • component (e) is used as component (e).
  • component (e) is usually used for the targeted manufactured industrial carbon black the English term carbon black, sometimes even the older term carbon black.
  • Carbon black is a modification of carbon with a very high surface area and is mainly used as a black pigment.
  • Internationally standard is the classification of standard blacks according to the US ASTM standard. Preference is given to carbon black having an average particle size in the range from 5 to 60 nm, particularly preferably in the range from 10 to 40 nm and very particularly preferably in the range from 10 to 40 nm Range of 15 and 25 nm used.
  • the carbon blacks to be used according to the invention CAS No.
  • component (e) are preferably used as powder or beads.
  • carbon blacks are selected from the group of ASTM standards N220, N234, N294, N330, N326, N347, N440, N472, N539, N550, N568, N601, N660, N762, N770, N785 , N880 and N990 (http://en.wikipedia.org/wiki/Ru%C3%9F).
  • Carbon black to be used as component (e) according to the invention is also referred to as black pigment (CI Pigment Black 7).
  • Nigrosine [ CAS No. 8005-03-6 ] is a mixture of synthetic black dyes (CI 50415, Solvent Black 5) and is prepared from a mixture of nitrobenzene, aniline and aniline hydrochloride in the presence of a copper or iron catalyst.
  • the main industrial applications are as colorants for paints and in marker pen inks.
  • Nigrosine is available, for example, from Kremer Pigmente GmbH & Co. KG, Aichstetten, Germany.
  • Further additives as component (f) for the purposes of the present invention are different from components (b) to (e) and preferably substances of the series thermal stabilizers, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers , Lubricants, mold release agents, dyes or pigments.
  • the above-mentioned and other suitable additives are state of the art and can be used by the person skilled in the art, for example in Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Kunststoff, 2001, pages 80-84, 546-547, 688, 872-874, 938, 966 be found.
  • the additives to be used as component (f) can be used alone or in mixture or in the form of masterbatches.
  • Additional heat stabilizers to be used according to the invention as additive (f) are copper compounds, in particular copper halides in combination with alkali metal halides and / or alkaline earth metal halides, preferably sodium chloride or calcium chloride, manganese chloride, sterically hindered phenols and / or phosphites, phosphates, preferably disodium dihydrogen diphosphate, hydroquinones, aromatic secondary amines, especially diphenylamines, substituted resorcinols, Salicylates, benzotriazoles or benzophenones, as well as various substituted representatives of these groups and / or mixtures thereof.
  • copper compounds in particular copper halides in combination with alkali metal halides and / or alkaline earth metal halides, preferably sodium chloride or calcium chloride, manganese chloride, sterically hindered phenols and / or phosphites, phosphates, preferably disodium dihydrogen diphosphate, hydroquinones,
  • Preferred UV stabilizers to be used as additive (f) according to the invention are substituted resorcinols, salicylates, benzotriazoles or benzophenones.
  • toughening modifiers or elastomer modifiers to be used as additive (f) are preferably copolymers which are preferably composed of at least two of the following series of monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene and acrylonitrile.
  • the copolymers may contain compatibilizing groups, preferably maleic anhydride or epoxide.
  • Dyes or pigments to be used as additive (f) according to the invention are preferably inorganic pigments, more preferably titanium dioxide, ultramarine blue, iron oxide or zinc sulfide, and organic pigments, more preferably phthalocyanines, quinacridones, perylenes and dyes, more preferably anthraquinones as colorants as well as other colorants.
  • Nucleating agents to be used as additive (f) according to the invention are preferably sodium or calcium phenylphosphinate, aluminum oxide or silicon dioxide or talc, particularly preferably talc.
  • Lubricants and / or mold release agents to be used according to the invention as additive (f) are preferably long-chain fatty acids, their salts, in particular Ca or Zn stearate and their ester derivatives or amide derivatives, in particular ethylenebis-stearylamide, glycerol tristearate, stearyl stearate, montan waxes, in particular esters of montan acids with ethylene glycol and low molecular weight polyethylene or polypropylene waxes in oxidized and non-oxidized form or, if not used as nucleating agent, talc.
  • long-chain fatty acids in particular Ca or Zn stearate and their ester derivatives or amide derivatives, in particular ethylenebis-stearylamide, glycerol tristearate, stearyl stearate, montan waxes, in particular esters of montan acids with ethylene glycol and low molecular weight polyethylene or polypropylene waxes in oxidized and non-oxidized form or,
  • Inventively particularly preferred lubricants and / or mold release agents are in the group of esters or amides of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated alcohols or amines having 2 to 40 carbon atoms.
  • Talcum preferably microcrystalline talcum, is particularly preferably used according to the invention.
  • Talcum [ CAS No. 14807-96-6 ], also referred to as talc, is a layered silicate with the chemical composition Mg 3 [Si 4 O 10 (OH) 2 ], which, depending on the modification, crystallizes as talc 1A in the triclinic or as talc 2M in the monoclinic crystal system (http: // /de.wikipedia.org/wiki/Talkum).
  • Talcum to be used according to the invention can be used, for example, as Mistron® R10 from Imerys Talc Group, Toulouse, France (Rio Tinto Group).
  • microcrystalline talc is understood as meaning a talc whose mean d 50 diameter is equal to or less than 4.5 microns. It is preferable to use a microcrystalline talc having a d95 cutting diameter equal to or smaller than 15 microns.
  • average d50 diameter is meant a diameter at which 50% by weight of the particles have a size of less than said diameter;
  • D 95 cut diameter is meant a diameter at which 95% by weight of the particles have a size of less than said diameter.
  • the size is determined by the equivalent spherical diameter (Stokes diameter).
  • compositions according to the invention or the thermoplastic molding compositions to be produced therefrom contain mixtures of the abovementioned lubricants and / or mold release agents.
  • the components (b) and (c) can be used in different proportions to each other. Preferred for the purposes of this invention are relative weight ratios of component (b) to component (c) between 5: 1 and 1: 5, more preferably between 3: 1 and 1: 3, most preferably between 2: 1 and 1: 2.
  • thermoplastic molding compositions can also be used in thermoplastic fiber composite materials.
  • the present invention therefore also thermoplastic fiber composites whose thermoplastic matrix contains the molding compositions of the invention.
  • Thermoplastic fiber composite materials in the context of the present invention are continuous fiber-reinforced semi-finished products, which are also referred to as organic sheets and are available, for example, from Bond-Laminates GmbH, Brilon, Germany under the TEPEX® brand. These organo sheets are completely impregnated and consolidated semi-finished products based on continuous fibers, in particular glass fibers, carbon fibers or aramid fibers.
  • a production process for organic sheets is for example off EP 1 923 420 A1 the contents of which are hereby fully incorporated by reference.
  • the present invention relates to thermoplastic molding compositions containing polyamide, preferably polyamide 6 or polyamide 66, dipentaerythritol, copolymer of ethene and C 4 -C 10 alkyl acrylate, preferably 2-ethylhexyl acrylate, and at least one Montanwachsester.
  • the present invention relates to thermoplastic molding compositions comprising polyamide, preferably polyamide 6 or polyamide 66, dipentaerythritol, copolymer of ethene and C 4 -C 10 alkyl acrylate, preferably 2-ethylhexyl acrylate, at least one montan wax ester, carbon black and / or nigrosine, alkali bromide, preferably Potassium bromide, and copper halide, preferably copper (I) iodide.
  • polyamide preferably polyamide 6 or polyamide 66
  • dipentaerythritol copolymer of ethene and C 4 -C 10 alkyl acrylate, preferably 2-ethylhexyl acrylate
  • at least one montan wax ester carbon black and / or nigrosine
  • alkali bromide preferably Potassium bromide
  • copper halide preferably copper (I) iodide.
  • blow molding in the first process step, plastic granules are drawn in by means of a heated extruder, compacted, degassed, heated, plasticized and homogenized to give a plastic plastic strand.
  • the plastic compound is fed into a hose head flanged to the extruder.
  • the plastic melt is formed into a tube that emerges vertically from a nozzle down.
  • the hose diameter is adapted to the article to be manufactured with different sizes of mandrel and nozzle flanges, which are flanged to the hose head.
  • the tube thickness and the resulting weight of the blow molded parts is predetermined by the selection of different diameter differences from mandrel to nozzle.
  • the method of injection molding is characterized in that the raw material, that is to be processed thermoplastic molding composition containing the mixtures according to the invention, preferably in granular form, melted (plasticized) in a heated cylindrical cavity and injected as a spray mass under pressure in a tempered cavity. After cooling (solidification) of the mass, the injection molded part is removed from the mold.
  • An injection molding machine consists of a clamping unit, the injection unit, the drive and the controller.
  • the clamping unit includes fixed and movable platens for the tool, a face plate and columns and drive of the moving platen. (Toggle joint or hydraulic clamping unit).
  • An injection unit comprises the electrically heatable cylinder, the drive of the worm (motor, gearbox) and the hydraulic system for moving the worm and injection unit.
  • the task of the injection unit is to melt the powder or the granules, to dose, to inject and to press (because of contraction).
  • the problem of melt backflow within the screw (leakage flow) is solved by backflow stops.
  • the present invention also relates to products, preferably moldings, shaped bodies, fibers or semi-finished products obtainable by extrusion or injection molding of the thermoplastic molding compositions according to the invention.
  • the present invention relates to the use of the molding compositions according to the invention for the production of articles in the electrical, electronics, telecommunications, information technology, solar, computer, household, sports, medical or entertainment industries, in particular preferred for motor vehicles, most preferably for the engine compartment of motor vehicles.
  • the present application also relates to the use of the molding compositions according to the invention in extrusion, preferably in the extrusion process or in profile extrusion, in injection molding or in blow molding for the production of products, preferably of molded parts or semi-finished products.
  • the subject matter is also the use of at least one polyol having at least two and at most 12 hydroxyl groups per molecule and an average molecular weight in the range from 64 to 2000 g / mol in combination with at least one copolymer of at least one olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol with a melt flow index (MFI) measured at 190 ° C and a load of 2.16 kg in the range of 100 g / 10 min to 800 g / 10 min for reducing or preventing thermo-oxidative damage to or from polyamide-based molding compositions Molded polyamide based products.
  • MFI melt flow index
  • thermoplastic molding compositions according to the invention and the components of the comparative examples were mixed in a twin-screw extruder of the ZSK 26 compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany) at a temperature of about 280 ° C., discharged as a strand into a water bath, cooled to Granulierpres and granulated. The granules were dried at 70 ° C in a vacuum oven to constant weight.
  • the granules were molded on an injection molding machine of the type Arburg SG370-173732 at melt temperatures in the range of 270 to 300 ° C and mold temperatures in the range of 80 to 100 ° C to shoulder bars (4mm thickness according to ISO 528) and plates with the dimensions 400 • 250 • 1.5 mm 3 (example 1 and comp. Example 1) as well as plates with the dimensions 60 • 4 • 4 mm 3 (example 2 and comp. Examples 2 and 3).
  • the mechanical properties of the products prepared from the inventive compositions in Example 2 and from the compositions for Comparative Examples 2 and 3 were determined in a tensile test according to ISO 527. The stability against thermooxidative damage is tested by storage of the specimens at 200 ° C for 1008 h followed by tensile testing.
  • the viscosity of the thermoplastic molding compositions in Example 1 (not according to the invention) and the viscosity of the molding composition for Comparative Example 1 in the molten state was determined using a capillary viscometer according to ISO 11443 at a temperature of 290 ° C.
  • the viscosity of the thermoplastic molding compositions in Example 2 and Comparative Examples 2 and 3 in the molten state was determined as a volume flow index according to DIN EN ISO 1133-1 at a temperature of 290 ° C with a preheating time of 10 minutes and a load weight of 5 kg.
  • Example 1 Plates in Example 1 (not according to the invention) and Comparative Example 1 were exposed to two different humid climatic conditions.
  • the plates were stored for 48 h at 90% relative humidity (RH) and 85 ° C and for 168 h at 90% RH and 40 ° C.
  • the plates in Example 2 and Comparative Examples 2 and 3 were stored for up to 672 hours at 85% RH and 85 ° C.
  • the deposit formation after storage was rated with a coating index between 1 and 6. In this case, a coating index of 1 means that no coating has been formed.
  • a covering index of 3 stands for a clearly visible but thin surface.
  • a covering index of 6 means a massive deposit formation over the whole plate.
  • compositions shown in Tables 1 and 2 below were all processed and tested as described above.
  • thermoplastic molding compositions of Comparative Example 1 show a clear deposit formation under both tested climatic conditions.
  • the viscosity of the molding composition is not increased by adding the copolymer. From this it can be concluded that the flow-improving effect of dipentaerythritol is not reduced by the addition of the copolymer.

Description

Die vorliegende Erfindung betrifft thermoplastische Formmassen auf Basis wenigstens eines Polyamids enthaltend mindestens ein Polyol und mindestens ein Copolymerisat aus mindestens einem Olefin mit mindestens einem Methacrylsäurester oder Acrylsäureester eines aliphatischen Alkohols. Des Weiteren betrifft diese Erfindung Erzeugnisse, insbesondere Fasern, Folien und Formteile aus diesen Formmassen und deren Verwendung. Zusätzlich betrifft diese Erfindung die Verwendung der beanspruchten Copolymerisate zur Reduktion der Belagsbildung von Polyamid-Formmassen bzw. auf den aus diesen Formmassen erhältlichen Erzeugnissen, die mindestens ein Polyol der Reihe Pentaerythrit, Dipentaerythrit und Tripentaerythrit enthalten.The present invention relates to thermoplastic molding compositions based on at least one polyamide containing at least one polyol and at least one copolymer of at least one olefin with at least one methacrylic acid ester or acrylic ester of an aliphatic alcohol. Furthermore, this invention relates to products, in particular fibers, films and moldings from these molding compositions and their use. In addition, this invention relates to the use of the claimed copolymers to reduce the deposit formation of polyamide molding compositions or on the products obtainable from these molding compositions containing at least one polyol of the series pentaerythritol, dipentaerythritol and tripentaerythritol.

Stand der TechnikState of the art

Polyamide werden häufig als Werkstoffe für Formteile eingesetzt, die während ihrer Lebensdauer erhöhten Temperaturen über einen längeren Zeitraum ausgesetzt sind. Für eine Vielzahl von Anwendungen ist es dabei erforderlich, dass die Werkstoffe ausreichend stabil gegenüber thermooxidativer Schädigung sind, die im Laufe der Lebenszeit eines aus diesen Werkstoffen hergestellten Erzeugnisses auftreten kann, insbesondere bei Anwendung solcher Erzeugnisse im Motorraum von Kraftfahrzeugen.
Polyamide zeigen im Allgemeinen eine Verschlechterung ihrer mechanischen Eigenschaften, wenn sie über einen längeren Zeitraum erhöhten Temperaturen ausgesetzt werden. Dieser Effekt basiert primär auf der oxidativen Schädigung des Polymers bei erhöhten Temperaturen (thermooxidative Schädigung). Ein längerer Zeitraum im Sinne der vorliegenden Erfindung bedeutet länger als 100 Stunden, erhöhte Temperaturen im Sinne der vorliegenden Erfindung bedeutet höher als 80 °C.
Die Stabilität thermoplastischer Formmassen gegen thermooxidative Schädigung wird üblicherweise durch den Vergleich mechanischer Eigenschaften beurteilt, insbesondere durch Vergleich der im Zugversuch nach ISO 527 gemessenen Bruchspannung und Bruchdehnung bei definierter Temperatur über einen definierten Zeitraum.
Zahlreiche Systeme zur Stabilisierung von Polymeren gegen thermooxidative Schädigung und dem daraus resultierenden molekularen Abbau sind bekannt und wurden in der Literatur beschrieben. Eine Zusammenfassung findet sich im " Plastic Additives Handbook" ,5th Edition, Herausgeber: Hans Zweifel, Carl Hanser Verlag, München 2001 , auf den Seiten 10 bis 19 und 40 bis 92. In technischen Thermoplasten, insbesondere Polyamiden, werden üblicherweise Antioxidantien auf Basis sterisch gehinderter Phenole oder auf Basis aromatischer Amine als organische Stabilisatoren oder Systeme auf Basis von Kupferverbindungen als anorganische Stabilisatoren eingesetzt. Die genannten organischen Stabilisatoren werden im Allgemeinen bei Temperaturen bis ca. 120 °C eingesetzt, einige sind auch bei höheren Temperaturen noch wirksam. Eine effektive Stabilisierung bei höheren Temperaturen bis ca. 140 °C wird üblicherweise durch Stabilisatorsysteme auf Basis von Mischungen aus Kupferhalogeniden und Alkalihalogeniden erreicht.Polyamides are often used as materials for moldings that are exposed to elevated temperatures over a longer period during their lifetime. For a variety of applications, it is necessary that the materials be sufficiently stable to the thermo-oxidative damage that may occur during the lifetime of a product made from these materials, particularly when such products are used in the engine compartment of motor vehicles.
Polyamides generally show a deterioration in their mechanical properties when exposed to elevated temperatures for extended periods of time. This effect is based primarily on the oxidative damage of the polymer at elevated temperatures (thermo-oxidative damage). A longer period in the sense of the present invention means longer than 100 hours, elevated temperatures in the sense of the present invention means higher than 80 ° C.
The stability of thermoplastic molding compositions to thermo-oxidative damage is usually assessed by comparing mechanical properties, in particular by comparing the tensile stress at break and elongation at break at a defined temperature measured in the tensile test according to ISO 527 over a defined period of time.
Numerous systems for stabilizing polymers against thermo-oxidative damage and the resulting molecular degradation are known and have been described in the literature. A summary can be found in the " Plastic Additives Handbook ", 5th Edition, publisher: Hans Zweifel, Carl Hanser Verlag, Munich 2001 , pages 10 to 19 and 40 to 92. In engineering thermoplastics, especially polyamides, be Usually antioxidants based on sterically hindered phenols or based on aromatic amines used as organic stabilizers or systems based on copper compounds as inorganic stabilizers. The said organic stabilizers are generally used at temperatures up to about 120 ° C, some are still effective at higher temperatures. An effective stabilization at higher temperatures up to about 140 ° C is usually achieved by stabilizer systems based on mixtures of copper halides and alkali halides.

In den letzten Jahren sind die Anforderungen an die Gebrauchstemperaturen, bei denen Polyamide noch ausreichend stabil sind, deutlich gestiegen. In vielen Anwendungen ist eine Langzeitwärmestabilisierung gegen thermooxidativen Abbau bei 160°C ja sogar bei Temperaturen bis in den Bereich von 180 bis 200°C gefordert. Im Rahmen der vorliegenden Erfindung wurde als Langzeit für die Versuche eine Dauer im Bereich von 1000 +/- 10 Stunden festgelegt. Die Zugabe von Polyolen zu Polyamid-basierten Formmassen stellt eine Möglichkeit dar, um Polyamide für die Verwendung bei Temperaturen im Bereich von 180 bis 200 °C zu stabilisieren. Besonders die Polyole Pentaerythrit, Dipentaerythrit und Tripentaerythrit haben sich als potente Stabilisatoren bei derartigen Temperaturen erwiesen.In recent years, the demands on the service temperatures at which polyamides are still sufficiently stable, have increased significantly. In many applications, a long-term heat stabilization against thermal oxidative degradation at 160 ° C yes even at temperatures up to the range of 180 to 200 ° C required. In the context of the present invention, a duration in the range of 1000 +/- 10 hours was defined as the long-term for the experiments. The addition of polyols to polyamide-based molding compositions provides a way to stabilize polyamides for use at temperatures ranging from 180 to 200 ° C. Especially the polyols pentaerythritol, dipentaerythritol and tripentaerythritol have proven to be potent stabilizers at such temperatures.

WO2010/014785 A1 beschreibt Polyamid-Formmassen, die durch Zugabe von Polyolen, besonders Dipentaerythrit und Tripentaerythrit, für Temperaturen bis 230 °C stabilisiert werden. WO2010 / 014785 A1 describes polyamide molding compositions which are stabilized by the addition of polyols, especially dipentaerythritol and tripentaerythritol, for temperatures up to 230 ° C.

WO2011/014556 A1 lehrt, dass auch Polyamid-Formmassen auf Basis von Mischungen von teilaromatischen Polyamiden und amorphen Polyamiden mit diesen Polyolen stabilisiert werden können. WO2011 / 014556 A1 teaches that also polyamide molding compositions based on mixtures of partially aromatic polyamides and amorphous polyamides can be stabilized with these polyols.

CN102030982 A beschreibt ein Stabilisatorsystem für Polyamidformmassen, welches aus einem elementaren Metall und Polyolen, insbesondere Dipentaerythrit, besteht. CN102030982 A describes a stabilizer system for polyamide molding compounds, which consists of an elemental metal and polyols, in particular dipentaerythritol.

Des Weiteren werden kurzkettige Polyole üblicherweise auch zur Verbesserung der Fließfähigkeit von Polyamid-basierten Formmassen eingesetzt.Furthermore, short-chain polyols are usually also used to improve the flowability of polyamide-based molding compositions.

So beschreibt EP 1041109 A2 Polyamid-basierte Formmassen, deren Fließfähigkeit durch die Zugabe von Polyolen, besonders auch von Pentaerythrit und Dipentaerythrit, deutlich verbessert wird ohne die mechanischen Eigenschaften der Formmassen deutlich zu verschlechtern.So describes EP 1041109 A2 Polyamide-based molding compositions whose flowability is significantly improved by the addition of polyols, especially of pentaerythritol and dipentaerythritol, without significantly deteriorating the mechanical properties of the molding compositions.

WO2010/014785 A1 beschreibt die Bereitstellung thermoplastischer Artikel auf Basis beispielsweise von Polyamid (6T/DT), einem Polyol, Glasfasern sowie weiterer Additive, die stabil gegenüber thermooxidativer Schädigung sind. WO2010 / 014785 A1 describes the provision of thermoplastic articles based on, for example, polyamide (6T / DT), a polyol, glass fibers and other additives which are stable to thermo-oxidative damage.

WO2007/036929 A1 beschreibt einen Prozess zur Produktion von Polyamid-Harzen mit verbesserter Fließfähigkeit, in dem Polyol, besonders auch Pentaerythrit, dem Polyamid während der Polymerisation zugegeben wird. WO2007 / 036929 A1 describes a process for the production of polyamide resins with improved flowability, in which polyol, especially pentaerythritol, is added to the polyamide during the polymerization.

Derartige Polyamid-basierte Formmassen, die Polyole enthalten, haben jedoch den Nachteil, dass die Polyole unter feuchten Klimabedingungen teilweise an die Oberfläche migrieren. Feuchte Klimabedingungen im Sinne dieser Erfindung liegen vor, wenn die Temperatur höher als 25 °C und die relative Luftfeuchtigkeit höher als 65 % ist. Diese Migration führt zur Bildung von Belägen auf den Oberflächen von Formteilen, Fasern oder Folien, die aus solchen Polyamid-Formmassen gefertigt werden. Derartige Oberflächenbeläge stören das ästhetische Empfinden des Kunden und können auch die Haftung von Klebstoffen oder Dichtmitteln erheblich reduzieren.However, such polyamide-based molding compositions containing polyols have the disadvantage that the polyols partially migrate to the surface under humid climatic conditions. Humid climatic conditions for the purposes of this invention are when the temperature is higher than 25 ° C and the relative humidity higher than 65%. This migration leads to the formation of coatings on the surfaces of moldings, fibers or films, which are made from such polyamide molding compounds. Such surface coverings disturb the aesthetic sensibility of the customer and can also significantly reduce the adhesion of adhesives or sealants.

Aufgabe der vorliegenden Erfindung war daher die Bereitstellung von Zusammensetzungen und daraus herzustellender thermoplastischer Formmassen auf Basis von Polyamid, welche Polyole enthalten und somit eine verbesserte Stabilität gegen thermooxidative Schädigung sowie eine verbesserte Fließfähigkeit bieten, aber gleichzeitig in deutlich geringerem Maße unter feuchten Klimabedingungen Oberflächenbeläge bilden.The object of the present invention was therefore to provide compositions based on polyamide and polyamide-based thermoplastic molding compositions which thus provide improved stability against thermo-oxidative damage and improved flowability, but at the same time form surface coatings to a much lesser extent under humid climatic conditions.

Die Fließfähigkeit thermoplastischer Formmassen wird üblicherweise durch den Vergleich der Schmelzeviskosität oder des Volumenfließindex beurteilt. Die Schmelzeviskosität wird im Allgemeinen und auch im Rahmen der vorliegenden Erfindung in einem Kapillar-Viskosimeter gemäß ISO 11443 bestimmt. Niedrige Werte für die Schmelzeviskosität deuten auf eine gute Fließfähigkeit hin. Hierbei ist der Scherratenbereich bei ca. 1000 1/s bis 1500 1/s besonders relevant für Aussagen über die Fließfähigkeit im Spritzgussprozess. Der Volumenfließindex wird im Allgemeinen und auch im Rahmen der vorliegenden Erfindung gemäß DIN EN ISO 1133-1 bei definierter Temperatur und definiertem Belastungsgewicht bestimmt. Ein hoher Wert für den Volumenfließindex deutet auf eine gute Fließfähigkeit hin.The flowability of thermoplastic molding compositions is usually assessed by comparing the melt viscosity or the volume flow index. The melt viscosity is determined in general and also in the context of the present invention in a capillary viscometer according to ISO 11443. Low melt viscosity values indicate good flowability. Here, the shear rate range at about 1000 1 / s to 1500 1 / s is particularly relevant for statements about the flowability in the injection molding process. The volume flow index is determined in general and also in the context of the present invention according to DIN EN ISO 1133-1 at a defined temperature and defined load weight. A high value for the volume flow index indicates a good flowability.

Die Verwendung von Copolymerisaten aus mindestens einem Olefin mit mindestens einem Methacrylsäurester oder Acrylsäureester eines aliphatischen Alkohols als Fließverbesserer Polyamid basierter Formmassen ist aus WO 2005/121249 A1 bekannt.The use of copolymers of at least one olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol as flow improver of polyamide-based molding compositions is made WO 2005/121249 A1 known.

Überraschenderweise wurde gefunden, dass mit mindestens einem Copolymerisat aus mindestens einem Olefin mit mindestens einem Methacrylsäureester oder Acrylsäureester eines aliphatischen Alkohols die Migration der Polyole unter feuchten Klimabedingungen deutlich verringert werden kann, ohne die positiven Effekte der Polyole auf Fließfähigkeit und Stabilität gegen thermooxidativen Abbau signifikant zu reduzieren. Die Stabiliät gegen thermooxidativen Abbau wurde im Rahmen der vorliegenden Erfindung durch die Bruchspannung ermittelt. Die Bruchkraft ist ein in der Werkstoffprüfung verwendeter Begriff für die Kraft, die benötigt wird, um einen Prüfkörper zu brechen oder zu zerreißen. Die Bruchkraft wird meist als Kraft (in N) oder - auf die Querschnittsfläche der Probe bezogen - als Bruchspannung (in N/mm2) angegeben. Beim Zugversuch oder Biegeversuch wird sie definiert durch den Kraftabfall, der auftritt, wenn das Maximum der Kraft überschritten ist, bei der sich der Werkstoff noch elastisch verformt. Fällt die Kraft z. B. um 20 %, erkennt die Universalprüfmaschine, dass die Probe gebrochen ist. Die Bruchspannung σB wurde im Rahmen der vorliegenden Erfindung nach EN ISO 527-1 (ISO-Version Februar 2012) durch Zugversuche mit einer Zugprüfmaschine ermittelt (siehe auch: http://de.wikipedia.org/wiki/Zugpr%C3%BCfmaschine).Surprisingly, it has been found that with at least one copolymer of at least one olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol, the migration of the polyols under moist climatic conditions can be significantly reduced without significantly reducing the positive effects of the polyols on flowability and stability against thermo-oxidative degradation , The stability against thermooxidative degradation was in the context of the present invention by the Breaking voltage determined. Breaking force is a term used in materials testing for the force needed to break or tear a specimen. The tensile strength is usually as a force (in N) or - based on the cross-sectional area of the sample - as a breakdown voltage (in N / mm 2) indicated. In the tensile test or bending test, it is defined by the force drop that occurs when the maximum force is exceeded at which the material is still elastically deformed. If the force falls z. By 20%, the universal testing machine detects that the sample has broken. The breaking stress σ B was determined in the context of the present invention according to EN ISO 527-1 (ISO version February 2012) by tensile tests with a tensile testing machine (see also: http://de.wikipedia.org/wiki/Zugpr%C3%BCfmaschine ).

Erfindunginvention

Die Lösung der Aufgabe und somit Gegenstand der vorliegenden Erfindung ist daher die Verwendung von mindestens einem der oben genannten Copolymerisate zur Reduktion der Belagsbildung im Feuchtklima bei thermoplastischen Formmassen bzw. daraus herzustellenden Erzeugnissen, die Polyamid und mindestens ein Polyol enthalten, wobei die Polyole organische Moleküle mit mindestens zwei und maximal 12 Hydroxylgruppen pro Molekül und einer mittleren relativen Molekülmasse im Bereich von 64 bis 2000 g/mol sind, wobei im Falle des Einsatzes von Polyolen, die Gemische oligomerer und/oder polymerer Polyole sind, für diesen Bestandteil der Mischung an Stelle der relativen Molekülmasse das Zahlenmittel des Molekulargewichtes (Mn) gilt.The solution of the problem and thus the subject of the present invention is therefore the use of at least one of the abovementioned copolymers to reduce the formation of deposits in the humid climate in thermoplastic molding compositions or products to be produced therefrom containing polyamide and at least one polyol, the polyols having organic molecules at least two and at most 12 hydroxyl groups per molecule and a mean molecular weight in the range of 64 to 2000 g / mol, wherein in the case of the use of polyols which are mixtures of oligomeric and / or polymeric polyols, for this component of the mixture in place of molecular weight is the number average molecular weight (M n ) applies.

Gegenstand der Erfindung sind aber auch thermoplastische Formmassen enthaltend

  1. (a) 10 bis 99,8 Gew.-% mindestens eines Polyamids,
  2. (b) 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 10 Gew.-%, besonders bevorzugt 1 bis 8 Gew.-%, ganz besonders bevorzugt 2 bis 7 Gew.-% mindestens eines Polyols mit mindestens zwei und maximal 12 Hydroxylgruppen pro Molekül und einer mittleren relativen Molekülmasse im Bereich von 64 bis 2000 g/mol und
  3. (c) 0,1 bis 10 Gew-%, bevorzugt 0,5 bis 10 Gew-%, besonders bevorzugt 1 bis 9 Gew.-%, ganz besonders bevorzugt 2 bis 8 Gew.-% mindestens eines Copolymerisats aus mindestens einem Olefin mit mindestens einem Methacrylsäurester oder Acrylsäureester eines aliphatischen Alkohols, das einen Melt-Flow-Index (MFI) gemessen bei 190°C und einer Belastung von 2,16 kg im Bereich von 100 g / 10 min bis 800 g / 10 min aufweist, der Gehalt des Olefins im Copolymerisat (c) im Bereich von 50 bis 90 Gew.-% und der Gehalt der Acrylsäure- oder Methacrylsäureester im als Komponente (c) einzusetzenden Copolymerisat im Bereich von 10 bis 50 Gew.-% liegt, mit der Maßgabe, dass die Summe aller Gewichtsprozente stets 100 ergibt und im Falle des Einsatzes von Polyolen (b), die Gemische oligomerer und/oder polymerer Polyole sind, für diesen Bestandteil der Mischung an Stelle der relativen Molekülmasse das Zahlenmittel des Molekulargewichtes (Mn) die Grenze des Bereiches bestimmt, wobei der Anteil der Komponenten (a), (b) und (c) im Bereich von 50 bis 100 Gew.-% liegt und wobei es sich bei den weiteren Komponenten bzw. übrigen Bestandteilen um Zusatzstoffe handelt, die der Fachmann entsprechend dem späteren Einsatz der Erzeugnisse auswählt.
Die Zubereitung von Zusammensetzungen für eine weitere Nutzung erfolgt durch Mischen der als Edukte einzusetzenden Komponenten (a), (b) und (c) in wenigstens einem Mischwerkzeug. Hierdurch werden die erfindungsgemäßen Formmassen erhalten. Diese Formmassen - auch als thermoplastische Formmassen bezeichnet - können entweder ausschließlich aus den Komponenten (a), (b) und (c) bestehen, oder aber zusätzlich zu den Komponenten (a), (b) und (c) noch weitere Komponenten enthalten. In diesem Fall sind die Komponenten (a), (b) und (c) im Rahmen der angegebenen Mengenbereiche so zu variieren, dass die Summe aller Gewichtsprozente stets 100 ergibt. Bei den thermoplastischen Formmassen und daraus herzustellenden Erzeugnissen liegt der Anteil der Komponenten (a), (b) und (c) im Bereich von 50 bis 100 Gew,-%, besonders bevorzugt im Bereich von 90 bis 100 Gew.-%, vor, wobei es sich bei den weiteren Komponenten bzw. übrigen Bestandteilen um Zusatzstoffe handelt, die der Fachmann entsprechend dem späteren Einsatz der Erzeugnisse auswählt, bevorzugt aus wenigstens einer der im Folgenden definierten Komponenten (d) bis (f).
Zur Klarstellung sei angemerkt, dass vom Rahmen der vorliegenden Erfindung alle nachfolgend aufgeführten allgemeinen oder in Vorzugsbereichen genannten Definitionen und Parameter in beliebigen Kombinationen umfasst sind.However, the invention also relates to thermoplastic molding compositions containing
  1. (a) 10 to 99.8% by weight of at least one polyamide,
  2. (B) 0.1 to 10 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1 to 8 wt .-%, most preferably 2 to 7 wt .-% of at least one polyol having at least two and a maximum of 12 hydroxyl groups per molecule and an average molecular weight in the range of 64 to 2000 g / mol and
  3. (C) 0.1 to 10 wt%, preferably 0.5 to 10 wt%, more preferably 1 to 9 wt .-%, most preferably 2 to 8 wt .-% of at least one copolymer of at least one olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol having a melt flow index (MFI) measured at 190 ° C and a load of 2.16 kg in the range of 100 g / 10 min to 800 g / 10 min, the content of the olefin in the copolymer (c) is in the range from 50 to 90% by weight and the content of acrylic or methacrylic acid esters in the copolymer to be used as component (c) is in the range from 10 to 50% by weight, with the proviso that the sum of all percentages by weight always gives 100 and in the case of the use of polyols (b), which are mixtures of oligomeric and / or polymeric polyols, for this Component of the mixture in place of the molecular weight, the number average molecular weight (M n ) determines the limit of the range, wherein the proportion of components (a), (b) and (c) in the range of 50 to 100 wt .-% and wherein the other components or other constituents are additives which the person skilled in the art selects according to the later use of the products.
The preparation of compositions for further use is carried out by mixing the components (a), (b) and (c) to be used as starting materials in at least one mixing tool. As a result, the molding compositions according to the invention are obtained. These molding compositions - also referred to as thermoplastic molding compositions - can either consist exclusively of the components (a), (b) and (c), or else in addition to the components (a), (b) and (c) contain other components. In this case, the components (a), (b) and (c) are to be varied within the specified quantity ranges so that the sum of all weight percentages always equals 100. In the case of the thermoplastic molding compositions and products to be produced therefrom, the proportion of components (a), (b) and (c) is in the range from 50 to 100% by weight, particularly preferably in the range from 90 to 100% by weight, wherein the other components or other constituents are additives which the person skilled in the art selects according to the later use of the products, preferably from at least one of the components (d) to (f) defined below.
For the sake of clarification, it should be noted that all general or preferred definitions and parameters listed below are included in any combination within the scope of the present invention.

Bevorzugte Ausführungsformen der ErfindungPreferred embodiments of the invention

In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen thermoplastischen Formmassen zusätzlich zu den Komponenten (a) bis (c) noch (d) 5 bis 80 Gew.-% wenigstens eines Füll- oder Verstärkungsstoffes, bevorzugt Glasfasern oder Kohlefasern, besonders bevorzugt Glasfasern, wobei die Anteile wenigstens eine der Komponenten (a) bis (c) so zu reduzieren sind, dass die Summe aller Gewichtsprozente stets 100 ergibt.In a preferred embodiment, the thermoplastic molding compositions according to the invention in addition to the components (a) to (c) still contain (d) 5 to 80 wt .-% of at least one filler or reinforcing material, preferably glass fibers or carbon fibers, particularly preferably glass fibers, wherein the proportions at least one of the components (a) to (c) are to be reduced such that the sum of all weight percentages always equals 100.

In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen thermoplastischen Formmassen zusätzlich zu den Komponenten (a) bis (d) oder anstelle von (d) noch (e) 0,1 bis 20 Gew.-% wenigstens eine Form von Ruß und/oder Nigrosin, bevorzugt Ruß, wobei die Anteile wenigstens einer der Komponenten (a) bis (c) und gegebenenfalls (d) so zu reduzieren sind, dass die Summe aller Gewichtsprozente stets 100 ergibt.In a preferred embodiment, the inventive thermoplastic molding compositions in addition to the components (a) to (d) or instead of (d) still (e) 0.1 to 20 wt .-% of at least one form of carbon black and / or nigrosine, preferably carbon black, wherein the proportions of at least one of the components (a) to (c) and, if appropriate, (d) are to be reduced so that the sum of all weight percentages always equals 100.

In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen thermoplastischen Formmassen zusätzliche zu den Komponenten (a) bis (e) oder anstelle von (d) und/oder (e) noch (f) 0,1 bis 20 Gew.-% wenigstens eines weiteren, von den Komponenten (b), (c), (d) und (e) verschiedenen Inhaltsstoffes, wobei die Anteile wenigstens eine der Komponenten (a) bis (c) und gegebenenfalls (d) und/oder (e) so zu reduzieren sind, dass die Summe aller Gewichtsprozente stets 100 ergibt. Erfindungsgemäß bevorzugt sind thermoplastischen Formmassen enthaltend

  1. (a) 10 bis 94,3 Gew.-% mindestens eines Polyamids,
  2. (b) 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, besonders bevorzugt 1 bis 4 Gew.-% mindestens eines Polyols mit mindestens zwei und maximal 12 Hydroxylgruppen pro Molekül und einer mittleren relativen Molekülmasse im Bereich von 64 bis 2000 g/mol und
  3. (c) 0,5 bis 10 Gew-%, bevorzugt 0,5 bis 6 Gew.-%, besonders bevorzugt 1 bis 6 Gew.-% mindestens eines Copolymerisats aus mindestens einem Olefin mit mindestens einem Methacrylsäurester oder Acrylsäureester eines aliphatischen Alkohols das einen Melt-Flow-Index (MFI) gemessen bei 190°C und einer Belastung von 2,16 kg im Bereich von 100 g / 10 min bis 800 g / 10 min aufweist und
  4. (d) 5 bis 80 Gew.-%, bevorzugt 10 bis 70 Gew.-%, besonders bevorzugt 15 bis 65 Gew.-% wenigstens eines Füll- oder Verstärkungsstoffes, sowie
  5. (e) 0,1 bis 20 Gew.-% wenigstens einer Form von Ruß oder Nigrosin, bevorzugt wenigstens einer Form von Ruß, wobei die Summe aller Gewichtsprozente stets 100 ergibt und im Falle des Einsatzes von Polyolen (b), die Gemische oligomerer und/oder polymerer Polyole sind, für diesen Bestandteil der Mischung an Stelle der relativen Molekülmasse das Zahlenmittel des Molekulargewichtes (Mn) die Grenze des Bereiches bestimmt..
In a preferred embodiment, the thermoplastic molding compositions according to the invention contain additional to the components (a) to (e) or instead of (d) and / or (e) (f) 0.1 to 20% by weight of at least one other ingredient other than components (b), (c), (d) and (e), the proportions comprising at least one of components (a) to (c ) and, if appropriate, (d) and / or (e) are to be reduced so that the sum of all weight percentages always equals 100. Preference according to the invention is given to thermoplastic molding compositions
  1. (a) 10 to 94.3% by weight of at least one polyamide,
  2. (B) 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, particularly preferably 1 to 4 wt .-% of at least one polyol having at least two and at most 12 hydroxyl groups per molecule and an average molecular weight in the range of 64 to 2000 g / mol and
  3. (C) 0.5 to 10% by weight, preferably 0.5 to 6 wt .-%, particularly preferably 1 to 6 wt .-% of at least one copolymer of at least one olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol, the one Melt Flow Index (MFI) measured at 190 ° C and a load of 2.16 kg in the range of 100 g / 10 min to 800 g / 10 min and has
  4. (D) 5 to 80 wt .-%, preferably 10 to 70 wt .-%, particularly preferably 15 to 65 wt .-% of at least one filler or reinforcing material, and
  5. (e) 0.1 to 20 wt .-% of at least one form of carbon black or nigrosine, preferably at least one form of carbon black, wherein the sum of all weight percent always 100 and in the case of the use of polyols (b), the mixtures oligomeric and or polymeric polyols, for this component of the mixture in place of the molecular weight, the number average molecular weight (M n ) determines the limit of the range.

Erfindungsgemäß bevorzugt sind aber auch thermoplastischen Formmassen enthaltend

  1. (a) 10 bis 94,2 Gew.-% mindestens eines Polyamids,
  2. (b) 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, besonders bevorzugt 1 bis 4 Gew.-% mindestens eines Polyols mit mindestens zwei und maximal 12 Hydroxylgruppen pro Molekül wobei dessen mittlere relative Molekülmasse im Bereich von 64 bis 2000 g/mol liegt und
  3. (c) 0,5 bis 10 Gew-%, bevorzugt 0,5 bis 6 Gew.-%, besonders bevorzugt 1 bis 6 Gew.-% mindestens eines Copolymerisats aus mindestens einem Olefin mit mindestens einem Methacrylsäurester oder Acrylsäureester eines aliphatischen Alkohols das einen Melt-Flow-Index (MFI) gemessen bei 190°C und einer Belastung von 2,16 kg im Bereich von 100 g / 10 min bis 800 g / 10 min aufweist und
  4. (d) 5 bis 80 Gew.-%, bevorzugt 10 bis 70 Gew.-%, besonders bevorzugt 15 bis 65 Gew.-% wenigstens eines Füll- oder Verstärkungsstoffes, sowie
  5. (e) 0,1 bis 20 Gew.-% wenigstens einer Form von Ruß oder Nigrosin, bevorzugt wenigstens einer Form von Ruß, sowie
  6. (f) 0,1 bis 20 Gew.-% wenigstens eines weiteren, von den Komponenten (b), (c), (d) und (e) verschiedenen Zusatzstoffes, wobei die Summe aller Gewichtsprozente stets 100 ergibt und im Falle des Einsatzes von Polyolen (b), die Gemische oligomerer und/oder polymerer Polyole sind, für diesen Bestandteil der Mischung an Stelle der relativen Molekülmasse das Zahlenmittel des Molekulargewichtes (Mn) die Grenze des Bereiches bestimmt.
According to the invention, however, thermoplastic molding compositions are also preferred
  1. (a) 10 to 94.2% by weight of at least one polyamide,
  2. (B) 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, particularly preferably 1 to 4 wt .-% of at least one polyol having at least two and at most 12 hydroxyl groups per molecule, wherein its average molecular weight is in the range of 64 to 2000 g / mol and
  3. (C) 0.5 to 10% by weight, preferably 0.5 to 6 wt .-%, particularly preferably 1 to 6 wt .-% of at least one copolymer of at least one olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol, the one Melt Flow Index (MFI) measured at 190 ° C and a load of 2.16 kg in the range of 100 g / 10 min to 800 g / 10 min and has
  4. (D) 5 to 80 wt .-%, preferably 10 to 70 wt .-%, particularly preferably 15 to 65 wt .-% of at least one filler or reinforcing material, and
  5. (E) 0.1 to 20 wt .-% of at least one form of carbon black or nigrosine, preferably at least one form of carbon black, and
  6. (f) 0.1 to 20% by weight of at least one further additive other than components (b), (c), (d) and (e), the sum of all percentages by weight always being 100 and in the case of use of polyols (b) which are mixtures of oligomeric and / or polymeric polyols, for this constituent of the mixture, in place of the molecular weight, the number average molecular weight (M n ) determines the limit of the range.

Die vorliegende Erfindung betrifft den Einsatz der thermoplastischen Formmassen im Spritzguss, im Blasformen oder in der Extrusion zur Herstellung von Erzeugnissen, insbesondere Fasern, Folien oder Formkörpern, jeglicher Art.The present invention relates to the use of the thermoplastic molding compositions in injection molding, in blow molding or in extrusion for the production of products, in particular fibers, films or moldings, of any kind.

Die vorliegende Erfindung betrifft des Weiteren die Verwendung dieser Erzeugnisse zur Herstellung von Artikeln für die Elektro-, Elektronik-, Telekommunikations-, Informationstechnologie-, Solar-, Computerindustrie, für den Haushalt, für den Sport, für medizinische Anwendungen oder für die Unterhaltungsindustrie, besonders bevorzugt für Kraftfahrzeuge, ganz besonders bevorzugt für den Motorraum von Kraftfahrzeugen.The present invention further relates to the use of these products for the manufacture of articles for the electrical, electronics, telecommunications, information technology, solar, computer, household, sports, medical or entertainment industries preferred for motor vehicles, most preferably for the engine compartment of motor vehicles.

Komponente (a)Component (a)

Die als Komponente (a) einzusetzenden Polyamide können amorphe Polyamide, semikristalline Polyamide oder teilkristalline Polyamide sein. Die als Komponente (a) einzusetzenden Polyamide sind bevorzugt teilkristalline Polyamide, besonders bevorzugt teilkristalline Polyamide mit einem Schmelzpunkt von mindestens 180 °C.The polyamides to be used as component (a) may be amorphous polyamides, semicrystalline polyamides or partially crystalline polyamides. The polyamides to be used as component (a) are preferably partially crystalline polyamides, particularly preferably semi-crystalline polyamides having a melting point of at least 180 ° C.

Die in einer Ausführungsform als Komponente (a) einzusetzenden teilkristallinen Polyamide werden bevorzugt ausgewählt aus der Gruppe PA6, PA66, PA610, PA612, PA10, PA810, PA106, PA1010, PA11, PA1011, PA1012, PA1210; PA1212, PA814, PA1014, PA618, PA512, PA613, PA813, PA914, PA1015, PA11, PA12 oder einem teilaromatischen Polyamid, einem sogenannten Polyphthalamid (PPA). Bevorzugte PPAs sind PA66/6T, PA6/6T, PA6T/MPMDT (MPMD steht für 2-Methylpentamethylendiamin), PA9T, PA10T, PA11T, PA12T, PA14T sowie Copolykondensate dieser letzten Typen mit einem aliphatischen Diamin und einer aliphatischen Dicarbonsäure oder mit einer α,ω-Aminocarbonsäure bzw. einem Lactam. Teilkristalline Polyamide besitzen gemäß DE 10 2011 084 519 A1 eine Schmelzenthalpie von mehr als 25 J/g, gemessen mit der DSC-Methode gemäß ISO11357 beim 2. Aufheizen und Integration des Schmelzpeaks. Erfindungsgemäß besonders bevorzugt wird als teilkristallines Polyamid der Komponente (a) PA6 oder PA66 oder ein Copolyamid von PA6 oder PA66 eingesetzt.The semicrystalline polyamides to be used in one embodiment as component (a) are preferably selected from the group PA6, PA66, PA610, PA612, PA10, PA810, PA106, PA1010, PA11, PA1011, PA1012, PA1210; PA1212, PA814, PA1014, PA618, PA512, PA613, PA813, PA914, PA1015, PA11, PA12 or a partly aromatic polyamide, a so-called polyphthalamide (PPA). Preferred PPAs are PA66 / 6T, PA6 / 6T, PA6T / MPMDT (MPMD stands for 2-methylpentamethylenediamine), PA9T, PA10T, PA11T, PA12T, PA14T and copolycondensates of these last types with an aliphatic diamine and an aliphatic dicarboxylic acid or with an α, ω-aminocarboxylic acid or a lactam. Semicrystalline polyamides according to DE 10 2011 084 519 A1 have a melting enthalpy of more than 25 J / g, measured by the DSC method according to ISO11357 during the 2nd heating and integration of the melt peak. Particularly preferred according to the invention is used as the partially crystalline polyamide of component (a) PA6 or PA66 or a copolyamide of PA6 or PA66.

Das in einer Ausführungsform als Komponente (a) einzusetzende semikristalline Polyamid besitzt gemäß DE 10 2011 084 519 A1 eine Schmelzenthalpie im Bereich von 4 bis 25 J/g, gemessen mit der DSC-Methode gemäß ISO 11357 beim 2. Aufheizen und Integration des Schmelzpeaks. Bevorzugte semikristalline Polyamide sind solche, die ausgehend von Diaminen und Dicarbonsäuren und/oder Lactamen mit wenigstens 5 Ringgliedern oder entsprechenden Aminosäuren hergestellt werden. Als Edukte kommen bevorzugt aliphatische und/oder aromatische Dicarbonsäuren, besonders bevorzugt Adipinsäure, 2,2,4-Trimethyladipinsäure, 2,4,4-Trimethyladipinsäure, Azelainsäure, Sebazinsäure, Isophthalsäure, Terephthalsäure, aliphatische und/oder aromatische Diamine, besonders bevorzugt Tetramethylendiamin, Hexamethylendiamin, 2-Methylpentan-1,5-diamin, 1,9-Nonandiamin, 2,2,4- und 2,4,4-Trimethylhexamethylendiamin, die Isomeren Diamino-dicyclohexylmethan, Diaminodicyclohexylpropan, Bis-aminomethyl-cyclohexan, Phenylendiamin, Xylylendiamin, Aminocarbonsäuren, insbesondere Aminocapronsäure, oder die entsprechenden Lactame in Betracht. Copolyamide aus mehreren der genannten Monomeren sind eingeschlossen.The semicrystalline polyamide to be used in one embodiment as component (a) has according to DE 10 2011 084 519 A1 a melting enthalpy in the range of 4 to 25 J / g, measured by the DSC method according to ISO 11357 at the 2nd heating and integration of the melt peak. Preferred semicrystalline polyamides are those which are prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids. Suitable starting materials are aliphatic and / or aromatic dicarboxylic acids, more preferably adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or aromatic diamines, particularly preferably tetramethylenediamine, Hexamethylenediamine, 2-methylpentane-1,5-diamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomers diamino-dicyclohexylmethane, diaminodicyclohexylpropane, bis-aminomethyl-cyclohexane, phenylenediamine, xylylenediamine , Aminocarbonsäuren, in particular aminocaproic acid, or the corresponding lactams into consideration. Copolyamides of several of the monomers mentioned are included.

In einer bevorzugten Ausführungsform wird als Komponente (a) auch ein Blend unterschiedlicher Polyamide eingesetzt. Insbesondere besonders bevorzugt sind weiterhin die meisten auf PA6, PA66 und andere auf aliphatischen oder/und aromatischen Polyamiden bzw. Copolyamiden basierenden Compounds, bei denen auf eine Polyamidgruppe in der Polymerkette 3 bis 11 Methylengruppen kommen.In a preferred embodiment, a blend of different polyamides is used as component (a). Most particularly preferred are most PA6, PA66 and other based on aliphatic or / and aromatic polyamides or copolyamides compounds in which come to a polyamide group in the polymer chain 3 to 11 methylene groups.

Die im Rahmen der vorliegenden Anmeldung benutzte Kennzeichnung der Polyamide entspricht internationaler Norm, wobei die erste(n) Ziffer(n) die C-Atomzahl des Ausgangsdiamins und die letzte(n) Ziffer(n) die C-Atomzahl der Dicarbonsäure angeben. Wird nur eine Zahl angegeben, wie im Falle des PA6, so bedeutet dies, dass von einer α,ω- Aminocarbonsäure bzw. von dem davon abgeleiteten Lactam, im Falle des PA6 also dem ε-Caprolactam, ausgegangen worden ist; im Übrigen sei verwiesen auf H. Domininghaus, Die Kunststoffe und ihre Eigenschaften, Seiten 272 ff., VDI-Verlag, 1976.The used in the present application marking the polyamides corresponds to international standard, wherein the first digit (s) indicate the C atomic number of Ausgangsdiamins and the last digit (s) the C atomic number of the dicarboxylic acid. If only one number is given, as in the case of PA6, this means that an α, ω-aminocarboxylic acid or the lactam derived therefrom, in the case of PA6, ie ε-caprolactam, has been used as starting material; Incidentally, reference is made to H. Domininghaus, The Plastics and their properties, pages 272 et seq., VDI-Verlag, 1976.

Bevorzugt wird als Komponente (a) mindestens ein teilkristallines Polyamid mit einer Viskositätszahl bestimmt in einer 0,5 gew.-%igen Lösung in 96 gew.-%iger Schwefelsäure bei 25 °C gemäß ISO 307 im Bereich von 80 bis 180 ml/g, besonders bevorzugt im Bereich von 90 bis 160 ml/g eingesetzt.Preferably, as component (a) at least one partially crystalline polyamide having a viscosity number determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307 in the range of 80 to 180 ml / g , more preferably used in the range of 90 to 160 ml / g.

Die in einer Ausführungsform einzusetzenden amorphen Polyamide besitzen gemäß DE 10 2011 084 519 A1 eine Schmelzenthalpie von weniger als 4 J/g, gemessen mit der DSC-Methode gemäß ISO 11357 beim 2. Aufheizen und Integration des Schmelzpeaks. Erfindungsgemäß einzusetzende amorphe Polyamide werden in der DE 10 2008 046 682 A1 beschrieben, die wiederum auf GB-PS 619 707 , US-PS 2494 563 , US-PS 26 96 482 , US-PS 25 16 585 , US-PS 38 47 877 , DE-OS 15 95 354 , US-PS 35 97 400 , US-PS 38 42 045 , CH-PS 4 49 257 , DE-OS 24 05 985 , DE-OS 29 36 759 . EP 0 012 931 , DE-PS 26 42 244 und US-PS 42 93 687 verweist, deren Inhalte beispielhafte amorphe Polyamide im Sinne der vorliegenden Erfindung offenbaren. Die in den erfindungsgemäßen thermoplastischen Formmassen einzusetzenden Polyamide können nach verschiedenen Verfahren hergestellt und aus unterschiedlichen Bausteinen synthetisiert werden. Zur Herstellung von Polyamiden sind eine Vielzahl von Verfahrensweisen bekannt, wobei je nach gewünschtem Endprodukt unterschiedliche Monomerbausteine sowie, verschiedene Kettenregler zur Einstellung eines angestrebten Molekulargewichtes, oder auch verschiedene Monomere mit entsprechenden reaktiven Gruppen für später beabsichtigte Nachbehandlungen eingesetzt werden.
Die technisch relevanten Verfahren zur Herstellung der erfindungsgemäß als Komponente (a) einzusetzenden Polyamide verlaufen meist über die Polykondensation in der Schmelze. Im Rahmen der vorliegenden Erfindung wird auch die hydrolytische Polymerisation von Lactamen als Polykondensation verstanden.The amorphous polyamides to be used in one embodiment have according to DE 10 2011 084 519 A1 a melting enthalpy of less than 4 J / g, measured by the DSC method according to ISO 11357 at the 2nd heating and integration of the melting peak. According to be used amorphous polyamides are in the DE 10 2008 046 682 A1 described, in turn GB-PS 619 707 . U.S. Patent 2,494,563 . US-PS 26 96 482 . US-PS 25 16 585 . U.S. Patent No. 3,847,877 . DE-OS 15 95 354 . US-PS 35 97 400 . US-PS 38 42 045 . CH-PS 4 49 257 . DE-OS 24 05 985 . DE-OS 29 36 759 , EP 0 012 931 . DE-PS 26 42 244 and US-PS 42 93 687 refers whose contents reveal exemplary amorphous polyamides in the context of the present invention. The polyamides to be used in the thermoplastic molding compositions according to the invention can be prepared by various processes and synthesized from different building blocks. For the preparation of polyamides, a variety of procedures are known, depending on the desired end product different monomer units and, different chain regulators for setting a desired molecular weight, or different monomers with corresponding reactive groups for later intended aftertreatments are used.
The technically relevant processes for the preparation of the polyamides to be used according to the invention as component (a) usually proceed via the polycondensation in the melt. In the context of the present invention, the hydrolytic polymerization of lactams is understood as polycondensation.

Komponente (b)Component (b)

Die als Komponente (b) erfindungsgemäß einzusetzenden Polyole sind auch bekannt unter den Bezeichnungen "Polyalkohol" oder "mehrwertiger Alkohol". Bei dem wenigstens einen erfindungsgemäß als Komponente (b) einzusetzenden Polyol handelt sich um organische Moleküle mit mindestens 2 und maximal 12 Hydroxylgruppen pro Molekül, wobei die mittlere relative Molekülmasse des Polyols bzw. der Polyole im Bereich von 64 bis 2000 g/mol liegt. Bevorzugt werden Polyole mit mindestens 3 und maximal 10 Hydroxylgruppen pro Molekül eingesetzt, besonders bevorzugt mit mindestens 4 und maximal 8 Hydroxylgruppen pro Molekül. Im Falle des Einsatzes von Polyolen (b), die Gemische oligomerer und/oder polymerer Polyole sind, wird für diesen Bestandteil der Mischung an Stelle der relativen Molekülmasse das Zahlenmittel des Molekulargewichtes (Mn) für die Festlegung der Grenzen des beanspruchten Bereiches eingesetzt.
Das als Komponente (b) einzusetzende wenigstens eine Polyol hat bevorzugt einen aliphatischen oder aromatischen Aufbau bzw. eine Kombination dieser beiden Merkmale. In einer alternativ bevorzugten Ausführungsform enthalten die aliphatischen Ketten innerhalb eines erfindungsgemäß als Komponente (b) einzusetzenden Polyols neben Kohlenstoffatomen auch Heteroatome, bevorzugt Stickstoff, Sauerstoff oder Schwefel. Die erfindungsgemäß einzusetzenden Polyole haben in einer bevorzugten Ausführungsform neben den Hydroxylgruppen außerdem weitere funktionelle Gruppen, bevorzugt Ethergruppen, Carbonsäuregruppen, Amidgruppen oder Estergruppen.
Besonders bevorzugt als Komponente (b) einzusetzende Polyole mit mehr als zwei Hydroxylgruppen sind solche Polyole mit drei Hydroxylgruppen der Gruppe Glyzerin, Trimethylolpropan, 2,3-Di-(2'-hydroxyethyl)-cyclohexan-1-ol, Hexan-1,2,6-triol, 1,1,1-Tris-(hydroxymethyl)ethan, 3-(2'-Hydroxyethoxy)-propan-1,2-diol, 3-(2'-Hydroxypropoxy)-propan-1,2-diol, 2-(2'-Hydroxyethoxy)-hexan-1,2-diol, 6-(2'-Hydroxypropoxy)-hexan-1,2-diol, 1,1,1-Tris-[(2'-hydroxyethoxy)-methyl]-ethan, 1,1,1-Tris-2'-hydroxypropoxy-methyl-propan, 1,1,1-Tris-(4'-hydroxyphenyl)-ethan, 1,1,1-Tris-(hydroxyphenyl)-propan, 1,1,3-Tris-(dihydroxy-3-methylphenyl)-propan, 1,1,4-Tris-(dihydroxyphenyl)-butan, 1,1,5-Tris-(hydroxyphenyl)-3-methylpentan, Di-trimethylolpropan, Ethoxylate und Propoxylate des Trimethylolpropans. Besonders bevorzugt als Komponente (b) einzusetzende Polyole mit mehr als drei Hydroxylgruppen sind Polyole der Reihe D-Mannit, D-Sorbit, Dulcit, Arabit, Inosit, Xylit, Talitol, Allitol, Altritol, Adonit, Erythrit, Threit, Pentaerythrit, Dipentaerythrit und Tripentaerythrit, sowie Polyole aus der Gruppe der Monosaccharide, insbesondere Mannose, Glucose, Galactose, Fructose, D-Xylose, Arabinose, D-Idose, D-Erythrose, D-Threose, D-Ribose, D-Lyxose, D-Allose, D-Altrose, D-Gulose, D-Talose, D-Ribulose, D-Erythrulose, D-Xylulose, D-Psicose, D-Sorbose, D-Tagatose, D-Gluconsäure, D-Zuckersäure, D-Mannozuckersäure, Schleimsäure, D-Glucuronsäure, D-Mannonsäure, Ascorbinsäure, D-Glucosamin, D-Galactosamin.
Insbesondere besonders bevorzugt als Komponente (b) einzusetzende Polyole sind solche mit mehr als drei Hydroxylgruppen. Ganz besonders bevorzugt wird wenigstens ein Polyol der Reihe Pentaerythrit, Dipentaerythrit, Tripentaerythrit und Di-Trimethylolpropan eingesetzt, insbesondere besonders bevorzugt sind Pentaerythrit, Dipentaerythrit und Tripentaerythrit, insbesondere ganz besonders bevorzugt ist Dipentaerythrit.The polyols to be used according to the invention as component (b) are also known under the names "polyalcohol" or "polyhydric alcohol". The at least one polyol to be used according to the invention as component (b) comprises organic molecules having at least 2 and at most 12 hydroxyl groups per molecule, the average molecular weight of the polyol or polyols being in the range from 64 to 2000 g / mol. Preference is given to using polyols having at least 3 and at most 10 hydroxyl groups per molecule, more preferably having at least 4 and not more than 8 hydroxyl groups per molecule. In the case of the use of polyols (b), which are mixtures of oligomeric and / or polymeric polyols, the number average molecular weight (M n ) is used instead of the molecular weight for this component of the mixture for the determination of the limits of the claimed range.
The at least one polyol to be used as component (b) preferably has an aliphatic or aromatic structure or a combination of these two features. In an alternatively preferred embodiment, the aliphatic chains within a polyol to be used according to the invention as component (b) contain not only carbon atoms but also heteroatoms, preferably nitrogen, oxygen or sulfur. In a preferred embodiment, the polyols to be used according to the invention also have, in addition to the hydroxyl groups, further functional groups, preferably ether groups, carboxylic acid groups, amide groups or ester groups.
Particularly preferred as component (b) polyols having more than two hydroxyl groups are those polyols having three hydroxyl groups of the group glycerol, trimethylolpropane, 2,3-di (2'-hydroxyethyl) cyclohexan-1-ol, hexane-1,2 , 6-triol, 1,1,1-tris (hydroxymethyl) ethane, 3- (2'-hydroxyethoxy) -propane-1,2-diol, 3- (2'-hydroxypropoxy) -propane-1,2- diol, 2- (2'-hydroxyethoxy) -hexane-1,2-diol, 6- (2'-hydroxypropoxy) -hexane-1,2-diol, 1,1,1-tris - [(2'-hydroxyethoxy ) -methyl] -ethane, 1,1,1-tris-2'-hydroxypropoxy-methyl-propane, 1,1,1-tris (4'-hydroxyphenyl) -ethane, 1,1,1-tris ( hydroxyphenyl) -propane, 1,1,3-tris (dihydroxy-3-methylphenyl) -propane, 1,1,4-tris (dihydroxyphenyl) -butane, 1,1,5-tris (hydroxyphenyl) -3 -methylpentane, di-trimethylolpropane, ethoxylates and propoxylates of trimethylolpropane. Polyols of the series D-mannitol, D-sorbitol, dulcitol, arabitol, inositol, xylitol, talitol, allitol, altritol, adonite, erythritol, threitol, pentaerythritol, dipentaerythritol and others which are particularly preferred as component (b) are polyols Tripentaerythritol, and polyols from the group of monosaccharides, especially mannose, glucose, galactose, fructose, D-xylose, arabinose, D-idose, D-erythrose, D-threose, D-ribose, D-lyxose, D-allose, D -Altrose, D-gulose, D-talose, D-ribulose, D-erythrulose, D-xylulose, D-psicose, D-sorbose, D-tagatose, D-gluconic acid, D-suberic acid, D-manno-sugic acid, mucic acid, D Glucuronic acid, D-mannonic acid, ascorbic acid, D-glucosamine, D-galactosamine.
Particularly particularly preferred as component (b) polyols to be used are those having more than three hydroxyl groups. Very particular preference is given to using at least one polyol of the series pentaerythritol, dipentaerythritol, tripentaerythritol and di-trimethylolpropane, particular preference being given to pentaerythritol, dipentaerythritol and tripentaerythritol, in particular very particular preference to dipentaerythritol.

Komponente (c)Component (c)

Als Komponente (c) enthalten die erfindungsgemäßen thermoplastischen Formmassen wenigstens ein Coplymerisat, bevorzugt wenigstens ein statistisches Copolymerisat aus mindestens einem Olefin, bevorzugt α-Olefin, und mindestens einem Methacrylsäureester oder Acrylsäureester eines aliphatischen Alkohols, das einen Melt-Flow-Index (MFI) gemessen bei 190°C und einer Belastung von 2,16 kg von mindestens 100 g / 10 min aufweist. In einer bevorzugten Ausführungsform besteht das als Komponente (c) einzusetzende Copolymerisat zu weniger als 4 Gew.-%, besonders bevorzugt zu weniger als 1,5 Gew.-% und ganz besonders bevorzugt zu 0 Gew.-% aus Monomerbausteinen, die weitere reaktive funktionelle Gruppen, ausgewählt aus der Gruppe umfassend Epoxide, Oxetane, Anhydride, Imide, Aziridine, Furane, Säuren, Amine, Oxazoline, enthalten.As component (c), the novel thermoplastic molding compositions comprise at least one copolymer, preferably at least one random copolymer of at least one olefin, preferably α-olefin, and at least one methacrylic acid ester or acrylic ester of an aliphatic alcohol, which measures a melt flow index (MFI) at 190 ° C and a load of 2.16 kg of at least 100 g / 10 min. In a preferred embodiment, the copolymer to be used as component (c) consists of less than 4% by weight, more preferably less than 1.5% by weight and most preferably 0% by weight of monomer building blocks which are further reactive functional groups selected from the group comprising epoxides, oxetanes, anhydrides, imides, aziridines, furans, acids, amines, oxazolines.

Geeignete Olefine, bevorzugt α-Olefine als Bestandteil der als Komponente (c) einzusetzenden Copolymerisate weisen bevorzugt zwischen 2 und 10 Kohlenstoff-Atomen auf und können unsubstituiert oder mit einer oder mehreren aliphatischen, cycloaliphatischen oder aromatischen Gruppen substituiert sein.Suitable olefins, preferably α-olefins as constituent of the copolymers to be used as component (c), preferably have between 2 and 10 carbon atoms and may be unsubstituted or substituted by one or more aliphatic, cycloaliphatic or aromatic groups.

Bevorzugte Olefine sind ausgewählt aus der Gruppe umfassend Ethen, Propen, 1-Buten, 1-Penten, 1-Hexen, 1-Octen, 3-Methyl-1-penten. Besonders bevorzugte Olefine sind Ethen und Propen, ganz besonders bevorzugt ist Ethen.Preferred olefins are selected from the group comprising ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene. Particularly preferred olefins are ethene and propene, most preferably ethene.

Ebenfalls geeignet sind Mischungen der beschriebenen Olefine.Also suitable are mixtures of the olefins described.

In einer weiter bevorzugten Ausführungsform werden die weiteren reaktiven funktionellen Gruppen des Copolymerisats (c) ausschließlich über die Olefine in das Copolymer (c) eingebracht, wobei diese funktionellen Gruppen ausgewählt werden aus der Gruppe umfassend Epoxide, Oxetane, Anhydride, Imide, Aziridine, Furane, Säuren, Amine, Oxazoline.In a further preferred embodiment, the further reactive functional groups of the copolymer (c) are introduced exclusively via the olefins into the copolymer (c), these functional groups being selected from the group comprising epoxides, oxetanes, anhydrides, imides, aziridines, furans, Acids, amines, oxazolines.

Der Gehalt des Olefins am Copolymerisat (c) liegt im Bereich von 50 bis 90 Gew.-%, bevorzugt im Bereich von 55 bis 75 Gew.-%.The content of the olefin in the copolymer (c) is in the range of 50 to 90% by weight, preferably in the range of 55 to 75% by weight.

Das Copolymerisat (c) wird weiterhin definiert durch den zweiten Bestandteil neben dem Olefin. Als zweiter Bestandteil sind Alkylester der Acrylsäure oder Methacrylsäure geeignet, deren Alkylgruppe aus 5-30 Kohlenstoffatomen gebildet wird. Die Alkylgruppe kann dabei linear oder verzweigt sein sowie cycloaliphatische Gruppen enthalten, daneben auch durch eine oder mehrere Ether- oder Thioetherfunktionen substituiert sein. Geeignete Methacrylsäureester oder Acrylsäureester in diesem Zusammenhang sind auch solche, die aus einer Alkoholkomponente synthetisiert wurden, die auf Oligoethylenglycol oder Oligopropylenglycol mit nur einer Hydroxylgruppe und maximal 30 C-Atomen basieren.The copolymer (c) is further defined by the second component besides the olefin. As the second component, alkyl esters of acrylic acid or methacrylic acid whose alkyl group is formed of 5-30 carbon atoms are suitable. The alkyl group may be linear or branched and may contain cycloaliphatic groups, but may also be substituted by one or more ether or thioether functions. Suitable methacrylic esters or acrylates in this context are also those synthesized from an alcohol component based on oligoethylene glycol or oligopropylene glycol having only one hydroxyl group and at most 30 carbon atoms.

Bevorzugt wird die Alkylgruppe des Methacrylsäureesters oder des Acrylsäureesters ausgewählt aus der Gruppe umfassend 1-Pentyl, 1-Hexyl, 2-Hexyl, 3-Hexyl, 1-Heptyl, 3-Heptyl, 1-Octyl, 1-(2-Ethyl)-hexyl, 1-Nonyl, 1-Decyl, 1-Dodecyl, 1-Lauryl oder 1-Octadecyl. Bevorzugt sind Alkylgruppen mit 6 - 20 Kohlenstoffatomen. Besonders bevorzugt sind insbesondere auch verzweigte Alkylgruppen, die im Vergleich zu linearen Alkylgruppen gleicher Anzahl an Kohlenstoffatomen zu einer niedrigeren Glasübergangs-Temperatur TG führen.The alkyl group of the methacrylic acid ester or of the acrylic acid ester is preferably selected from the group comprising 1-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 1-heptyl, 3-heptyl, 1-octyl, 1- (2-ethyl) - hexyl, 1-nonyl, 1-decyl, 1-dodecyl, 1-lauryl or 1-octadecyl. Preference is given to alkyl groups having 6 to 20 carbon atoms. Particularly preferred are in particular also branched alkyl groups, which lead to a lower glass transition temperature TG compared to linear alkyl groups of the same number of carbon atoms.

Erfindungsgemäß besonders bevorzugt sind als Komponente (c) einzusetzende Copolymerisate auf Basis von Ethen und Acrylsäurealkylester, deren Alkylgruppe aus 5 - 10 Kohlenstoffatomen gebildet wird.Particular preference is given in accordance with the invention to copolymers which are to be used as component (c) and are based on ethene and alkyl acrylates whose alkyl group is formed from 5-10 carbon atoms.

Erfindungsgemäß ganz besonders bevorzugt sind Copolymerisate bei denen das Olefin, insbesondere Ethen, mit Acrylsäure-(2-ethyl)-hexylester copolymerisiert wird.Very particular preference according to the invention is given to copolymers in which the olefin, in particular ethene, is copolymerized with 2-ethylhexyl acrylate.

Ebenfalls geeignet sind Mischungen der beschriebenen Acrylsäureester oder Methacrylsäurester. Bevorzugt ist hierbei die Verwendung von mehr als 60 Gew.-%, besonders bevorzugt mehr als 90 Gew.-% und ganz besonders bevorzugt die Verwendung von 100 Gew.-% Acrylsäure-(2-ethyl)-hexylester bezogen auf die Gesamtmenge an Acrylsäure- und Methacrylsäurester im als Komponente (c) einzusetzenden Copolymerisat.Also suitable are mixtures of the described acrylic acid esters or methacrylic acid esters. Preferred here is the use of more than 60 wt .-%, more preferably more than 90 wt .-% and most preferably the use of 100 wt .-% of acrylic acid (2-ethyl) -hexylester based on the total amount of acrylic acid - And methacrylic acid in the component (c) to be used copolymer.

In einer weiter bevorzugten Ausführungsform werden die weiteren reaktiven funktionellen Gruppen des Copolymerisats (c) ausschließlich über die Acrylsäureester oder Methacrylsäureester in das als Komponente (c) einzusetzende Copolymer eingebracht, wobei die funktionellen Gruppen ausgewählt werden aus der Gruppe umfassend Epoxide, Oxetane, Anhydride, Imide, Aziridine, Furane, Säuren, Amine, Oxazoline .In a further preferred embodiment, the further reactive functional groups of the copolymer (c) are introduced exclusively via the acrylic acid esters or methacrylic acid esters into the copolymer to be used as component (c), wherein the functional groups are selected from the group comprising epoxides, oxetanes, anhydrides, imides , Aziridines, furans, acids, amines, oxazolines.

Der Gehalt der Acrylsäureester oder Methacrylsäureester im als Komponente (c) einzusetzenden Copolymerisat liegt im Bereich von 10 bis 50 Gew.-%, bevorzugt im Bereich von 25 bis 45 Gew.-%.The content of the acrylic acid esters or methacrylic acid esters in the copolymer to be used as component (c) is in the range from 10 to 50% by weight, preferably in the range from 25 to 45% by weight.

Als Komponente (c) einzusetzende Copolymerisate zeichnen sich neben der Zusammensetzung durch das niedrige Molekulargewicht aus. Dementsprechend sind für die erfindungsgemäßen Zusammensetzungen und die daraus erhältlichen Formmassen nur Copolymerisate als Komponente (c) geeignet, die einen Melt-Flow-Index (MFI) gemessen bei 190°C und einer Belastung von 2,16 kg im Bereich von 100 g / 10 min bis 800 g / 10 min aufweisen, bevorzugt im Bereich von 150 g / 10 min bis 800 g / 10 min, besonders bevorzugt im Bereich von 300 g / 10 min bis 700 g / 10 min.Copolymers to be used as component (c) are distinguished, in addition to the composition, by the low molecular weight. Accordingly, for the compositions according to the invention and the molding compositions obtainable therefrom, only copolymers suitable as component (c) having a melt flow index (MFI) measured at 190 ° C. and a load of 2.16 kg in the range of 100 g / 10 are suitable min to 800 g / 10 min, preferably in the range of 150 g / 10 min to 800 g / 10 min, more preferably in the range of 300 g / 10 min to 700 g / 10 min.

Als Komponente (c) geeignete Copolymerisate können ausgewählt sein aus der Gruppe der von der Fa. Arkema unter dem Markennamen Lotryl® EH angebotenen Materialien, die gewöhnlich als Schmelzkleber Verwendung finden. Erfindungsgemäß insbesondere bevorzugt ist ein Copolymerisat aus Ethen und Ethylhexylacrylat (EHA), das als Lotryl® 37 EH 550 [ CAS-No. 26984-27-0 ] von Arkema, Puteaux, Frankreich angeboten wird.Copolymers suitable as component (c) can be selected from the group of materials offered by Arkema under the brand name Lotryl® EH, which are usually used as hotmelt adhesives. Particularly preferred according to the invention is a copolymer of ethene and ethylhexyl acrylate (EHA), which is known as Lotryl® 37 EH 550 [ CAS-No. 26984-27-0 ] by Arkema, Puteaux, France.

Komponente (d)Component (d)

Füll- und Verstärkungsstoffe als Komponente (d) im Sinne der vorliegenden Erfindung sind faserförmige, nadelförmige oder teilchenförmige Füll- und Verstärkungsstoffe. Bevorzugt sind Glasfasern, Kohlenstofffasern, Glaskugeln, amorphe Kieselsäure, Calciumsilicat, Calciummetasilicat, Magnesiumcarbonat, Kaolin, calciniertes Kaolin, Kreide, gepulverter Quarz, Glimmer, Phlogopit, Bariumsulfat, Feldspat, Wollastonit, Montmorillonit, besonders bevorzugt Glasfasern, insbesondere bevorzugt Glasfasern aus E-Glas. Die faserförmigen oder teilchenförmigen Verstärkungsstoffe sind in einer bevorzugten Ausführungsform zur besseren Verträglichkeit mit dem als Komponente (a) einzusetzenden Polyamid mit geeigneten Oberflächenmodifizierungen, insbesondere Oberflächenmodifizierungen enthaltend Silanverbindungen versehen. Erfindungsgemäß werden für Komponente (d) geschnittene Glasfasern mit einer mittleren Ausgangslänge im Bereich von 1 bis 50 mm, besonders bevorzugt im Bereich von 1 bis 10 mm, ganz besonders bevorzugt im Bereich von 2 bis 7 mm eingesetzt. Die Glasfasern der Komponente (d) können bedingt durch die Verarbeitung zur Formmasse oder zum Erzeugnis in der Formmasse oder im Erzeugnis einen kleineren d97 bzw. d50-Wert aufweisen, als die ursprünglich eingesetzten Glasfasern. So liegt der arithmetische Mittelwert der Glasfaserlänge nach der Verarbeitung häufig nur noch im Bereich von 150 µm bis 300 µm. Der Medianwert oder d50-Wert ist als Maß für die mittlere Teilchengröße die wichtigste Kenngröße. 50 Volumen-Prozent der Probe sind feiner und die anderen 50% sind grober als d50. d25, d75 oder d97 sind analog definiert (Clariant Analytical Services, Technical Sheet 106).
Die erfindungsgemäß als Komponente (d) bevorzugt einzusetzenden Glasfasern [ CAS No. 65997-17-3 ] haben bevorzugt einen mittleren Faserdurchmesser im Bereich von 7 bis 18 µm, besonders bevorzugt im Bereich von 9 bis 15 µm, der durch wenigstens eine dem Fachmann zur Verfügung stehende Möglichkeit zu ermitteln ist. Die als Komponente (d) einzusetzenden Glasfasern werden bevorzugt als geschnittene oder als Endlosfasern oder gemahlene Glasfasern zugesetzt. Eine Längen- und Durchmesser- / Dickenbestimmung der Einzelfaser erfolgt im Rahmen der vorliegenden Erfindung halbautomatisch anhand rasterelektronenmikroskopischer Bilder (REM) mittels Grafiktableau und rechnergestützter Datenerfassung.
Die als Komponente (d) bevorzugt einzusetzenden Fasern, insbesondere Glasfasern, werden bevorzugt mit einem geeigneten Schlichtesystem oder einem Haftvermittler bzw. Haftvermittlersystem, besonders bevorzugt mit einem Haftvermittler auf Silanbasis, ausgerüstet.Fillers and reinforcing agents as component (d) for the purposes of the present invention are fibrous, needle-shaped or particulate fillers and reinforcing agents. Preference is given to glass fibers, carbon fibers, glass spheres, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, powdered quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite, particularly preferably glass fibers, particularly preferably glass fibers made of E glass , The fibrous or particulate reinforcing materials are provided in a preferred embodiment for better compatibility with the polyamide to be used as component (a) with suitable surface modifications, in particular surface modifications containing silane compounds. According to the invention, cut glass fibers having an average starting length in the range from 1 to 50 mm, particularly preferably in the range from 1 to 10 mm, very particularly preferably in the range from 2 to 7 mm, are used for component (d). The glass fibers of component (d) may have a smaller d97 or d50 value than the glass fibers originally used due to the processing to the molding compound or to the product in the molding compound or in the product. Thus, the arithmetic mean of the glass fiber length after processing is often only in the range of 150 microns to 300 microns. The median value or d50 value is the most important parameter as a measure of the mean particle size. 50% by volume of the sample is finer and the other 50% are coarser than d50. d25, d75 or d97 are defined analogously (Clariant Analytical Services, Technical Sheet 106).
The glass fibers preferably to be used according to the invention as component (d) CAS No. 65997-17-3 ] preferably have an average fiber diameter in the range from 7 to 18 μm, particularly preferably in the range from 9 to 15 μm, which can be determined by at least one option available to the person skilled in the art. The glass fibers to be used as component (d) are preferably added as cut or as continuous fibers or ground glass fibers. A determination of the length and diameter / thickness of the individual fiber takes place semi-automatically in the context of the present invention on the basis of scanning electron microscopic images (SEM) by means of a graphics tablet and computer-aided data acquisition.
The fibers preferably used as component (d), in particular glass fibers, are preferably provided with a suitable sizing system or an adhesion promoter or adhesion promoter system, particularly preferably with a silane-based adhesion promoter.

Ganz besonders bevorzugte Haftvermittler auf Silanbasis für die Ausrüstung der Füll- oder Verstärkungsstoffe, insbesondere Glasfasern, sind Silanverbindungen der allgemeinen Formel (I)

        (X-(CH2)q)k-Si-(O-CrH2r+1)4-k     (I)

in der die Substituenten folgende Bedeutung haben:

X:
NH2-, HO-,
Figure imgb0001
q:
eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4,
r:
eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2,
k:
eine ganze Zahl von 1 bis 3, bevorzugt 1.
Very particularly preferred silane-based adhesion promoters for finishing the fillers or reinforcing materials, in particular glass fibers, are silane compounds of the general formula (I)

(X- (CH 2 ) q ) k -Si (OC r H 2r + 1) 4 - k (I)

in which the substituents have the following meanings:
X:
NH 2 -, HO-,
Figure imgb0001
q:
an integer from 2 to 10, preferably 3 to 4,
r:
an integer from 1 to 5, preferably 1 to 2,
k:
an integer from 1 to 3, preferably 1.

Insbesondere bevorzugte Haftvermittler sind Silanverbindungen aus der Gruppe Aminopropyltrimethoxysilan, Aminobutyltrimethoxysilan, Aminopropyltriethoxysilan, Aminobutyltriethoxysilan sowie die entsprechenden Silane, welche als Substituent X in Formel (I) eine Glycidylgruppe enthalten.Particularly preferred adhesion promoters are silane compounds from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X in formula (I).

Für die Ausrüstung der insbesondere bevorzugt als Komponente (d) einzusetzenden Glasfasern werden die bevorzugt Silanverbindungen als Haftvermittler enthaltenden Schlichtesysteme bevorzugt in Mengen im Bereich von 0,05 bis 2 Gew.-%, besonders bevorzugt im Bereich von 0,25 bis 1,5 Gew.-% und insbesondere im Bereich von 0,5 bis 1 Gew.-% (Gew.-% nach Trocknung) bezogen auf die Glasfasern zur Oberflächenbeschichtung eingesetzt. Der Gewichtsanteil an Haftvermittlern, insbesondere Silanen, an der Oberflächenbeschichtung der Glasfasern beträgt bevorzugt 2 - 10 Gew.-% der Trockenmasse.For the finishing of the glass fibers to be used particularly preferably as component (d), the sizing compounds preferably containing silane compounds as adhesion promoter are preferably used in amounts ranging from 0.05 to 2% by weight, more preferably in the range from 0.25 to 1.5% by weight .-% and in particular in the range of 0.5 to 1 wt .-% (wt .-% after drying) based on the glass fibers used for surface coating. The proportion by weight of adhesion promoters, in particular silanes, in the surface coating of the glass fibers is preferably from 2 to 10% by weight of the dry matter.

Komponente (e)Component (s)

Erfindungsgemäß wird als Komponente (e) wenigstens eine Form von Ruß und/oder Nigrosin, insbesondere Ruß eingesetzt. Zur Unterscheidung wird für den gezielt hergestellten Industrie-Grundstoff Ruß meist der englische Begriff Carbon Black gebraucht, manchmal auch noch der ältere Begriff Industrieruß. Industrieruß ist eine Modifikation des Kohlenstoffs mit sehr hoher Oberfläche und wird vor allem als Schwarzpigment verwendet. International üblich ist die Klassifizierung von Standardrußen nach der US-amerikanischen ASTM-Norm. Bevorzugt wird Ruß mit einer mittleren Partikelgröße im Bereich von 5 und 60 nm, besonders bevorzugt im Bereich von 10 und 40 nm und ganz besonders bevorzugt im Bereich von 15 und 25 nm eingesetzt. Die erfindungsgemäß einzusetzenden Ruße [ CAS No. 1333-86-4 ] werden bevorzugt als Pulver oder Perlen eingesetzt. Ganz besonders bevorzugt als Komponente (e) einzusetzende Ruße werden ausgewählt aus der Gruppe der ASTM-Normen N220, N234, N294, N330, N326, N347, N440, N472, N539, N550, N568, N601, N660, N762, N770, N785, N880 und N990 (http://de.wikipedia.org/wiki/Ru%C3%9F). Erfindungsgemäß als Komponente (e) einzusetzender Ruß wird auch als Schwarz-Pigment (C. I. Pigment Black 7) bezeichnet. Weitere Typen sind erhältlich von Orion Carbons als Black Pigments PRINTEX, HIBLACK, AROSPERSE, NIPex, NEROX, COLOUR BLACK, SPECIAL BLACK, oder vom Hersteller Birla Carbon die Typen Raven, Conductex, Copeblack oder vom Hersteller Cabot die Typen BLACK PEARLS, ELFTEX, MOGUL, MONARCH, REGAL, SPHERON, STERLING, VULCAN, CSX, CRX, IRX, UNITED.According to the invention, at least one form of carbon black and / or nigrosine, in particular carbon black, is used as component (e). To distinguish between soot is usually used for the targeted manufactured industrial carbon black the English term carbon black, sometimes even the older term carbon black. Carbon black is a modification of carbon with a very high surface area and is mainly used as a black pigment. Internationally standard is the classification of standard blacks according to the US ASTM standard. Preference is given to carbon black having an average particle size in the range from 5 to 60 nm, particularly preferably in the range from 10 to 40 nm and very particularly preferably in the range from 10 to 40 nm Range of 15 and 25 nm used. The carbon blacks to be used according to the invention CAS No. 1333-86-4 ] are preferably used as powder or beads. Most preferably used as component (e) carbon blacks are selected from the group of ASTM standards N220, N234, N294, N330, N326, N347, N440, N472, N539, N550, N568, N601, N660, N762, N770, N785 , N880 and N990 (http://en.wikipedia.org/wiki/Ru%C3%9F). Carbon black to be used as component (e) according to the invention is also referred to as black pigment (CI Pigment Black 7). Other types are available from Orion Carbons as Black Pigments PRINTEX, HIBLACK, AROSPERSE, NIPex, NEROX, COLOR BLACK, SPECIAL BLACK, or by the manufacturer Birla Carbon the types Raven, Conductex, Copeblack or by the manufacturer Cabot the types BLACK PEARLS, ELFTEX, MOGUL , MONARCH, REGAL, SPHERON, STERLING, VULCAN, CSX, CRX, IRX, UNITED.

Nigrosin [ CAS No. 8005-03-6 ] ist eine Mischung synthetischer schwarzer Farbstoffe (CI 50415, Solvent Black 5) und wird aus einem Gemisch von Nitrobenzol, Anilin und Anilinhydrochlorid in Gegenwart eines Kupfer- oder Eisenkatalysators hergestellt. Die wichtigsten industriellen Anwendungen sind als Farbmittel für Lacke und in Marker-Stift-Tinten. Nigrosin ist beispielsweise erhältlich bei Kremer Pigmente GmbH & Co.KG, Aichstetten, Deutschland.Nigrosine [ CAS No. 8005-03-6 ] is a mixture of synthetic black dyes (CI 50415, Solvent Black 5) and is prepared from a mixture of nitrobenzene, aniline and aniline hydrochloride in the presence of a copper or iron catalyst. The main industrial applications are as colorants for paints and in marker pen inks. Nigrosine is available, for example, from Kremer Pigmente GmbH & Co. KG, Aichstetten, Germany.

Komponente (f)Component (f)

Weitere Zusatzstoffe als Komponente (f) im Sinne der vorliegenden Erfindung sind unterschiedlich zu den Komponenten (b) bis (e) und bevorzugt Stoffe der Reihe Thermostabilisatoren, UV-Stabilisatoren, Gammastrahlenstabilisatoren, Hydrolysestabilisatoren, Antistatika, Emulgatoren, Nukleierungsmittel, Weichmacher, Verarbeitungshilfsmittel, Schlagzähmodifikatoren, Gleitmittel, Entformungsmittel, Farbstoffe oder Pigmente. Die genannten und weitere geeignete Additive sind Stand der Technik und können vom Fachmann beispielsweise im Plastics Additives Handbook, 5th Edition, Hanser-Verlag, München, 2001, Seiten 80-84, 546-547, 688, 872-874, 938, 966 aufgefunden werden.Further additives as component (f) for the purposes of the present invention are different from components (b) to (e) and preferably substances of the series thermal stabilizers, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers , Lubricants, mold release agents, dyes or pigments. The above-mentioned and other suitable additives are state of the art and can be used by the person skilled in the art, for example in Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Munich, 2001, pages 80-84, 546-547, 688, 872-874, 938, 966 be found.

Die als Komponente (f) einzusetzenden Zusatzstoffe können alleine oder in Mischung bzw. in Form von Masterbatchen eingesetzt werden.The additives to be used as component (f) can be used alone or in mixture or in the form of masterbatches.

Erfindungsgemäß bevorzugt als Zusatzstoff (f) einzusetzende zusätzliche Thermostabilisatoren sind Kupferverbindungen, insbesondere Kupferhalogenide in Kombination mit Alkalimetallhalogeniden und/oder Erdalkalimetallhalogenide, bevorzugt Natriumchlorid oder Calciumchlorid, Manganchlorid, sterisch gehinderte Phenole und/oder Phosphite, Phosphate, bevorzugt Dinatriumdihydrogendiphosphat, Hydrochinone, aromatische sekundäre Amine, insbesondere Diphenylamine, substituierte Resorcine, Salicylate, Benzotriazole oder Benzophenone, sowie verschieden substituierte Vertreter dieser Gruppen und/oder deren Mischungen.Additional heat stabilizers to be used according to the invention as additive (f) are copper compounds, in particular copper halides in combination with alkali metal halides and / or alkaline earth metal halides, preferably sodium chloride or calcium chloride, manganese chloride, sterically hindered phenols and / or phosphites, phosphates, preferably disodium dihydrogen diphosphate, hydroquinones, aromatic secondary amines, especially diphenylamines, substituted resorcinols, Salicylates, benzotriazoles or benzophenones, as well as various substituted representatives of these groups and / or mixtures thereof.

Erfindungsgemäß bevorzugt als Zusatzstoff (f) einzusetzende UV-Stabilisatoren sind substituierte Resorcine, Salicylate, Benzotriazole oder Benzophenone.Preferred UV stabilizers to be used as additive (f) according to the invention are substituted resorcinols, salicylates, benzotriazoles or benzophenones.

Erfindungsgemäß als Zusatzstoff (f) einzusetzende Schlagzähmodifikatoren oder Elastomermodifikatoren sind unterschiedlich zur Komponente (c) bevorzugt Copolymerisate, die wiederum bevorzugt aus mindestens zwei der folgenden Reihe an Monomeren aufgebaut sind: Ethylen, Propylen, Butadien, Isobuten, Isopren, Chloropren, Vinylacetat, Styrol und Acrylnitril. Die Copolymerisate können kompatibilisierende Gruppen, bevorzugt Maleinsäureanhydrid oder Epoxid enthalten.In accordance with the invention, toughening modifiers or elastomer modifiers to be used as additive (f) are preferably copolymers which are preferably composed of at least two of the following series of monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene and acrylonitrile. The copolymers may contain compatibilizing groups, preferably maleic anhydride or epoxide.

Erfindungsgemäß als Zusatzstoff (f) einzusetzende Farbstoffe oder Pigmente sind unterschiedlich zur Komponente (e) bevorzugt anorganische Pigmente, besonders bevorzugt Titandioxid, Ultramarinblau, Eisenoxid oder Zinksulfid, sowie organische Pigmente, besonders bevorzugt Phthalocyanine, Chinacridone, Perylene sowie Farbstoffe, besonders bevorzugt Anthrachinone als Farbmittel sowie andere Farbmittel.Dyes or pigments to be used as additive (f) according to the invention are preferably inorganic pigments, more preferably titanium dioxide, ultramarine blue, iron oxide or zinc sulfide, and organic pigments, more preferably phthalocyanines, quinacridones, perylenes and dyes, more preferably anthraquinones as colorants as well as other colorants.

Erfindungsgemäß als Zusatzstoff (f) einzusetzende Nukleierungsmittel sind bevorzugt Natrium- oder Calciumphenylphosphinat, Aluminiumoxid oder Siliziumdioxid oder Talkum, besonders bevorzugt Talkum.Nucleating agents to be used as additive (f) according to the invention are preferably sodium or calcium phenylphosphinate, aluminum oxide or silicon dioxide or talc, particularly preferably talc.

Erfindungsgemäß als Zusatzstoff (f) einzusetzende Gleit- und/oder Entformungsmittel sind bevorzugt langkettige Fettsäuren, insbesondere Stearinsäure, deren Salze, insbesondere Ca- oder Zn-Stearat sowie deren Esterderivate oder Amidderivate, insbesondere Ethylenbis-stearylamid, Glyzerin-tristearat, Stearylstearat, Montanwachse, insbesondere Ester von Montansäuren mit Ethylenglycol sowie niedermolekulare Polyethylen- bzw. Polypropylenwachse in oxidierter und nicht-oxidierter Form oder, sofern nicht als Nukleierungsmittel eingesetzt, Talkum. Erfindungsgemäß besonders bevorzugte Gleit- und/oder Entformungsmittel sind in der Gruppe der Ester oder Amide gesättigter oder ungesättigter aliphatischer Carbonsäuren mit 8 bis 40 C-Atomen mit aliphatischen gesättigten Alkoholen oder Aminen mit 2 bis 40 C-Atomen enthalten.Lubricants and / or mold release agents to be used according to the invention as additive (f) are preferably long-chain fatty acids, their salts, in particular Ca or Zn stearate and their ester derivatives or amide derivatives, in particular ethylenebis-stearylamide, glycerol tristearate, stearyl stearate, montan waxes, in particular esters of montan acids with ethylene glycol and low molecular weight polyethylene or polypropylene waxes in oxidized and non-oxidized form or, if not used as nucleating agent, talc. Inventively particularly preferred lubricants and / or mold release agents are in the group of esters or amides of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated alcohols or amines having 2 to 40 carbon atoms.

Erfindungsgemäß besonders bevorzugt wird Talkum, bevorzugt mikrokristallines Talkum, eingesetzt. Talkum [ CAS No. 14807-96-6 ], auch als Talk bezeichnet, ist ein Schichtsilikat mit der chemischen Zusammensetzung Mg3[Si4O10(OH)2], das je nach Modifikation als Talk-1A im triklinen oder als Talk-2M im monoklinen Kristallsystem kristallisiert (http://de.wikipedia.org/wiki/Talkum). Erfindungsgemäß einzusetzendes Talkum kann beispielsweise als Mistron® R10 von Imerys Talc Group, Toulouse, Frankreich (Rio Tinto Group) bezogen werden. Erfindungsgemäß wird unter mikrokristallinem Talkum ein Talkum verstanden, dessen mittlerer d50-Durchmesser gleich oder kleiner als 4,5 Mikron ist. Es wird vorzugsweise ein mikrokristallines Talkum mit einem d95-Schnittdurchmesser von gleich oder kleiner als 15 Mikron verwendet.
Unter "mittlerer d50-Durchmesser" ist ein Durchmesser zu verstehen, bei dem 50 Gew.-% der Partikel eine Größe von weniger als dem genannten Durchmesser haben; unter "D95-Schnittdurchmesser" ist ein Durchmesser zu verstehen, bei dem 95 Gew.-% der Partikel eine Größe von weniger als dem genannten Durchmesser haben. Für nichtsphärische Partikel wird die Größe durch den äquivalenten sphärischen Durchmesser bestimmt (Stokes-Durchmesser). Alle diese d50- und d95-Durchmessermessungen werden mit einer Vorrichtung "Sédigraph" (Warenzeichen) durch Schwerkraftsedimentation gemäß der Norm AFNOR X11-683 durchgeführt. Standard-Talkum besitzt einen d50 in der Größenordnung von 8 bis 15 Mikron. In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zusammensetzungen bzw. die aus diesen herzustellenden thermoplastischen Formmassen Mischungen der oben genannten Gleit- und/oder Entformungsmittel.
Die Komponenten (b) und (c) können in unterschiedlichen Verhältnissen zueinander eingesetzt werden. Bevorzugt im Sinne dieser Erfindung sind relative Gewichtsverhältnisse der Komponente (b) zur Komponente (c) zwischen 5:1 und 1:5, besonders bevorzugt zwischen 3:1 und 1:3, ganz besonders bevorzugt zwischen 2:1 und 1:2.
Die erfindungsgemäßen thermoplastischen Formmassen können auch in thermoplastischen Faserverbundwerkstoffen Einsatz finden. Gegenstand der vorliegenden Erfindung sind daher auch thermoplastische Faserverbundwerkstoffe, deren thermoplastische Matrix die erfindungsgemäßen Formmassen enthält. Thermoplastische Faserverbundwerkstoffe im Sinne der vorliegenden Erfindung sind endlosfaserverstärkte Halbzeuge, die auch als Organobleche bezeichnet werden und beispielsweise bei der Firma Bond-Laminates GmbH, Brilon, Deutschland unter der Marke TEPEX® erhältlich sind. Es handelt sich bei diesen Organoblechen um vollständig imprägnierte und konsolidierte Halbzeuge auf Basis von Endlosfasern, insbesondere Glasfasern, Carbonfasern oder Aramidfasern. Ein Herstellungsverfahren für Organobleche ist beispielsweise aus EP 1 923 420 A1 bekannt, deren Inhalt hiermit vollumfänglich umfasst wird.Talcum, preferably microcrystalline talcum, is particularly preferably used according to the invention. Talcum [ CAS No. 14807-96-6 ], also referred to as talc, is a layered silicate with the chemical composition Mg 3 [Si 4 O 10 (OH) 2 ], which, depending on the modification, crystallizes as talc 1A in the triclinic or as talc 2M in the monoclinic crystal system (http: // /de.wikipedia.org/wiki/Talkum). Talcum to be used according to the invention can be used, for example, as Mistron® R10 from Imerys Talc Group, Toulouse, France (Rio Tinto Group). According to the invention, microcrystalline talc is understood as meaning a talc whose mean d 50 diameter is equal to or less than 4.5 microns. It is preferable to use a microcrystalline talc having a d95 cutting diameter equal to or smaller than 15 microns.
By "average d50 diameter" is meant a diameter at which 50% by weight of the particles have a size of less than said diameter; By "D 95 cut diameter" is meant a diameter at which 95% by weight of the particles have a size of less than said diameter. For non-spherical particles, the size is determined by the equivalent spherical diameter (Stokes diameter). All these d50 and d95 diameter measurements are made with a "Sédigraph" (trade mark) device by gravity sedimentation in accordance with the AFNOR X11-683 standard. Standard talc has a d50 on the order of 8 to 15 microns. In a further preferred embodiment, the compositions according to the invention or the thermoplastic molding compositions to be produced therefrom contain mixtures of the abovementioned lubricants and / or mold release agents.
The components (b) and (c) can be used in different proportions to each other. Preferred for the purposes of this invention are relative weight ratios of component (b) to component (c) between 5: 1 and 1: 5, more preferably between 3: 1 and 1: 3, most preferably between 2: 1 and 1: 2.
The novel thermoplastic molding compositions can also be used in thermoplastic fiber composite materials. The present invention therefore also thermoplastic fiber composites whose thermoplastic matrix contains the molding compositions of the invention. Thermoplastic fiber composite materials in the context of the present invention are continuous fiber-reinforced semi-finished products, which are also referred to as organic sheets and are available, for example, from Bond-Laminates GmbH, Brilon, Germany under the TEPEX® brand. These organo sheets are completely impregnated and consolidated semi-finished products based on continuous fibers, in particular glass fibers, carbon fibers or aramid fibers. A production process for organic sheets is for example off EP 1 923 420 A1 the contents of which are hereby fully incorporated by reference.

Ganz besonders bevorzugt betrifft die vorliegende Erfindung thermoplastische Formmassen enthaltend Polyamid, bevorzugt Polyamid 6 oder Polyamid 66, Dipentaerythrit, Copolymerisat aus Ethen und C4-C10 Alkylacrylat, bevorzugt 2-Ethylhexylacrylat, sowie wenigstens einen Montanwachsester.Most preferably, the present invention relates to thermoplastic molding compositions containing polyamide, preferably polyamide 6 or polyamide 66, dipentaerythritol, copolymer of ethene and C 4 -C 10 alkyl acrylate, preferably 2-ethylhexyl acrylate, and at least one Montanwachsester.

In einer Ausführungsform betrifft die vorliegende Erfindung thermoplastische Formmassen enthaltend Polyamid, bevorzugt Polyamid 6 oder Polyamid 66, Dipentaerythrit, Copolymerisat aus Ethen und C4-C10 Alkylacrylat, bevorzugt 2-Ethylhexylacrylat, wenigstens einen Montanwachsester, Ruß und/oder Nigrosin, Alkalibromid, bevorzugt Kaliumbromid, sowie Kupferhalogenid, bevorzugt Kupfer (I)-Iodid.In one embodiment, the present invention relates to thermoplastic molding compositions comprising polyamide, preferably polyamide 6 or polyamide 66, dipentaerythritol, copolymer of ethene and C 4 -C 10 alkyl acrylate, preferably 2-ethylhexyl acrylate, at least one montan wax ester, carbon black and / or nigrosine, alkali bromide, preferably Potassium bromide, and copper halide, preferably copper (I) iodide.

Verfahrenmethod

Ferner ist Gegenstand der vorliegenden Erfindung ein Verfahren zur Herstellung von Formmassen indem man die Komponenten (a) bis (c) sowie gegebenenfalls noch (d) und/oder (e) und/oder (f) in entsprechenden Gewichtsanteilen innerhalb der oben angegebenen Gewichtsprozente mischt, bevorzugt in wenigstens einem Mischaggregat. Bevorzugte Mischaggregate sind Buss-Kneter oder Zweiwellenextruder. Vorzugsweise geschieht das Mischen der Komponenten bei Temperaturen im Bereich von 220 bis 400°C, bevorzugt im Bereich von 220 bis 350 °C. Vorzugsweise erfolgt das Mischen durch gemeinsames Vermengen, Vermischen, Kneten, Compoundieren, Extrudieren oder Verwalzen der Komponenten. Besonders bevorzugt erfolgt das Mischen der Komponenten durch Compoundieren in wenigstens einem Mischaggregat, bevorzugt auf einem gleichläufigen Zweiwellenextruder oder Buss-Kneter. Es kann vorteilhaft sein, einzelne Komponenten vorzumischen.
Erfindungsgemäße Verfahren zur Herstellung von Erzeugnissen mittels Extrusion oder Spritzguss arbeiten bevorzugt bei Schmelzetemperaturen im Bereich von 230 bis 330°C, besonders bevorzugt im Bereich von 250 bis 300°C sowie gegebenenfalls zusätzlich bei Drücken von maximal 2500 bar, bevorzugt bei Drücken von maximal 2000 bar, besonders bevorzugt bei Drücken von maximal 1500 bar und ganz besonders bevorzugt bei Drücken von maximal 750 bar.
Bei der Extrusion, auch als Strangpressen bezeichnet, werden feste bis dickflüssige härtbare thermoplastische Formmassen unter Druck kontinuierlich aus einer formgebenden Öffnung, auch als Düse, Matrize oder Mundstück bezeichnet, hinaus gepresst. Dabei entstehen Erzeugnisse mit dem Querschnitt der Öffnung in theoretisch beliebiger Länge (http://de.wikipedia.org/wiki/Extrusion_(Verfahrenstechnik)). Die grundsätzlichen Verfahrensschritte des Profil-Extrusionsverfahrens, einer Verfahrensform der Extrusion, sind:

  1. 1. Plastifizieren und Bereitstellen der thermoplastischen Schmelze in einem Extruder,
  2. 2. Extrusion des thermoplastischen Schmelzestrangs durch eine Kalibrierhülse, die den Querschnitt des zu extrudierenden Profils aufweist,
  3. 3. Abkühlung des extrudierten Profils in einem Kalibriertisch,
  4. 4. Weitertransport des Profils mit einem Abzug hinter dem Kalibriertisch,
  5. 5. Ablängen des zuvor endlosen Profils in einer Schneideanlage,
  6. 6. Sammeln der abgelängten Profile an einem Sammeltisch.
The present invention further provides a process for the preparation of molding compositions by mixing the components (a) to (c) and optionally also (d) and / or (e) and / or (f) in corresponding proportions by weight within the weight percentages given above , preferably in at least one mixing unit. Preferred mixing units are Buss kneaders or twin-screw extruders. Preferably, the mixing of the components occurs at temperatures in the range of 220 to 400 ° C, preferably in the range of 220 to 350 ° C. Preferably, the mixing is carried out by mixing together, mixing, kneading, compounding, extruding or rolling the components. Particularly preferably, the mixing of the components takes place by compounding in at least one mixing unit, preferably on a co-rotating twin-screw extruder or Buss kneader. It may be advantageous to premix individual components.
Processes according to the invention for producing articles by means of extrusion or injection molding preferably operate at melt temperatures in the range from 230 to 330 ° C., more preferably in the range from 250 to 300 ° C. and optionally additionally at pressures of not more than 2500 bar, preferably at pressures of not more than 2000 bar , more preferably at pressures of at most 1500 bar and most preferably at pressures of at most 750 bar.
In extrusion, also referred to as extrusion, solid to viscous curable thermoplastic molding compositions under pressure continuously from a shaping opening, also referred to as a nozzle, die or mouthpiece, pressed out. This produces products with the cross section of the opening in theoretically any length (http://de.wikipedia.org/wiki/Extrusion_(Verfahrenstechnik)). The basic process steps of the profile extrusion process, a process form of extrusion, are:
  1. 1. plasticizing and providing the thermoplastic melt in an extruder,
  2. 2. extrusion of the thermoplastic melt strand through a calibration sleeve having the cross-section of the profile to be extruded,
  3. 3. cooling the extruded profile in a calibration table,
  4. 4. further transport of the profile with a trigger behind the calibration table,
  5. 5. cutting to length the previously endless profile in a cutting machine,
  6. 6. Collect the cut profiles at a collecting table.

Eine Beschreibung der Profilextrusion von Polyamid 6 und Polyamid 66 erfolgt im Kunststoff-Handbuch 3/4, Polyamide, Carl Hanser Verlag, München 1998, Seite 374-384 . Extrusionsanlagen zum Herstellen von Profilen bestehen aus: Extruder, Profil-Werkzeug, Kalibrierung, Kühlstrecke, Raupen- und Rollenabzug, Trennvorrichtung und Kipprinne.A description of the profile extrusion of polyamide 6 and polyamide 66 is given in Plastics Handbook 3/4, polyamides, Carl Hanser Verlag, Munich 1998, pages 374-384 , Extrusion lines for the production of profiles consist of: extruder, profile tool, calibration, cooling section, caterpillar and roller take-off, separating device and tilting channel.

Das Verfahren des Blasformens ist beispielsweise in http://www.blasformen.com/ beschrieben. Beim Blasformen wird im ersten Verfahrensschritt mittels eines beheizten Extruders Kunststoffgranulat eingezogen, verdichtet, entgast, aufgeheizt, plastifiziert und zu einem plastischen Kunststoffstrang homogenisiert.The method of blow molding is described, for example, in http://www.blasformen.com/. In blow molding, in the first process step, plastic granules are drawn in by means of a heated extruder, compacted, degassed, heated, plasticized and homogenized to give a plastic plastic strand.

Im nächsten Schritt wird die Kunststoffmasse in einen an den Extruder angeflanschten Schlauchkopf geführt. Dort wird die Kunststoffschmelze zu einem Schlauch geformt, der senkrecht aus einer Düse nach unten austritt.In the next step, the plastic compound is fed into a hose head flanged to the extruder. There, the plastic melt is formed into a tube that emerges vertically from a nozzle down.

Der Schlauchdurchmesser wird mit unterschiedlich großen Dorn- und Düsennormalien, die an den Schlauchkopf angeflanscht werden, an den zu fertigenden Artikel angepasst.The hose diameter is adapted to the article to be manufactured with different sizes of mandrel and nozzle flanges, which are flanged to the hose head.

Die Schlauchdicke und das daraus resultierende Gewicht der Blasformteile wird durch die Auswahl von unterschiedlichen Durchmesser- Differenzen von Dorn zu Düse vorbestimmt.The tube thickness and the resulting weight of the blow molded parts is predetermined by the selection of different diameter differences from mandrel to nozzle.

Das Verfahren des Spritzgusses zeichnet sich dadurch aus, dass der Rohstoff, also die zu verarbeitende thermoplastische Formmasse enthaltend die erfindungsgemäßen Mischungen, bevorzugt in Granulatform, in einem beheizten zylindrischen Hohlraum aufgeschmolzen (plastifiziert) und als Spritzmasse unter Druck in einem temperierten Hohlraum gespritzt wird. Nach dem Abkühlen (Erstarren) der Masse wird das Spritzgussteil entformt.The method of injection molding is characterized in that the raw material, that is to be processed thermoplastic molding composition containing the mixtures according to the invention, preferably in granular form, melted (plasticized) in a heated cylindrical cavity and injected as a spray mass under pressure in a tempered cavity. After cooling (solidification) of the mass, the injection molded part is removed from the mold.

Man unterscheidetOne differentiates

  1. 1. Plastifizieren / Aufschmelzen1. plasticizing / melting
  2. 2. Einspritzphase (Füllvorgang)2nd injection phase (filling process)
  3. 3. Nachdruckphase (wegen thermischer Kontraktion bei der Kristallisation)3rd post-pressure phase (due to thermal contraction during crystallization)
  4. 4. Entformen.4. Demoulding.

Eine Spritzgießmaschine besteht aus einer Schließeinheit, der Spritzeinheit, dem Antrieb und der Steuerung. Zur Schließeinheit gehören feste und bewegliche Aufspannplatten für das Werkzeug, eine Stirnplatte sowie Säulen und Antrieb der beweglichen Werkzeugaufspannplatte. (Kniehebelgelenk oder hydraulische Schließeinheit).An injection molding machine consists of a clamping unit, the injection unit, the drive and the controller. The clamping unit includes fixed and movable platens for the tool, a face plate and columns and drive of the moving platen. (Toggle joint or hydraulic clamping unit).

Eine Spritzeinheit umfasst den elektrisch beheizbaren Zylinder, den Antrieb der Schnecke (Motor, Getriebe) und die Hydraulik zum Verschieben der Schnecke und Spritzeinheit. Die Aufgabe der Spritzeinheit besteht darin, das Pulver bzw. das Granulat aufzuschmelzen, zu dosieren, einzuspritzen und nachzudrücken (wegen Kontraktion). Das Problem des Rückflusses der Schmelze innerhalb der Schnecke (Leckströmung) wird durch Rückstromsperren gelöst.An injection unit comprises the electrically heatable cylinder, the drive of the worm (motor, gearbox) and the hydraulic system for moving the worm and injection unit. The task of the injection unit is to melt the powder or the granules, to dose, to inject and to press (because of contraction). The problem of melt backflow within the screw (leakage flow) is solved by backflow stops.

Im Spritzgießwerkzeug wird dann die einströmende Schmelze gelöst, gekühlt und somit das zu fertigende Bauteil gefertigt. Notwendig dazu sind immer zwei Werkzeughälften. Beim Spritzguss unterscheidet man folgende Funktionskomplexe:

  • Angusssystem
  • Formbildende Einsätze
  • Entlüftung
  • Maschinen- und Kraftaufnahme
  • Entformungssystem und Bewegungsübertragung
  • Temperierung
In the injection mold then the inflowing melt is dissolved, cooled and thus manufactured the component to be manufactured. Necessary are always two tool halves. In injection molding, the following functional complexes are distinguished:
  • Angus system
  • Shaping inserts
  • vent
  • Machine and power consumption
  • Deformation system and motion transmission
  • tempering

Im Gegensatz zum Spritzguss wird bei der Extrusion ein endlos geformter Strang aus der erfindungsgemäßen thermoplastischen Formmasse im Extruder eingesetzt, wobei der Extruder eine Maschine zur Herstellung von Erzeugnissen auf Basis thermoplastischer Formstücke ist. Man unterscheidet

  • Einschneckenextruder und Doppelschneckenextruder sowie die jeweiligen Untergruppen
  • konventioneller Einschneckenextruder, förderwirksamer Einschneckenextruder,
  • gegenläufiger Doppelschneckenextruder und gleichläufiger Doppelschneckenextruder.
In contrast to injection molding, an endlessly shaped strand of the thermoplastic molding composition according to the invention is used in the extruder during the extrusion, the extruder being a machine for the production of products based on thermoplastic molded pieces. One differentiates
  • Single-screw extruders and twin-screw extruders and the respective subgroups
  • conventional single-screw extruder, single-screw extruder,
  • counter-rotating twin-screw extruder and co-rotating twin-screw extruder.

Erzeugnisseproduce

Die vorliegende Erfindung betrifft folglich auch Erzeugnisse, bevorzugt Formteile, Formkörper Fasern oder Halbzeuge, erhältlich durch Extrusion oder Spritzguss der erfindungsgemäßen thermoplastischen Formmassen.Consequently, the present invention also relates to products, preferably moldings, shaped bodies, fibers or semi-finished products obtainable by extrusion or injection molding of the thermoplastic molding compositions according to the invention.

Verwendungenuses

Die vorliegende Erfindung betrifft schließlich die Verwendung der erfindungsgemäßen Formmassen für die Herstellung von Artikeln der Elektro-, Elektronik-, Telekommunikations-, Informationstechnologie-, Solar-, Computerindustrie, für den Haushalt, für den Sport, für medizinische Anwendungen oder für die Unterhaltungsindustrie, besonders bevorzugt für Kraftfahrzeuge, ganz besonders bevorzugt für den Motorraum von Kraftfahrzeugen.Finally, the present invention relates to the use of the molding compositions according to the invention for the production of articles in the electrical, electronics, telecommunications, information technology, solar, computer, household, sports, medical or entertainment industries, in particular preferred for motor vehicles, most preferably for the engine compartment of motor vehicles.

Gegenstand der vorliegenden Anmeldung ist auch die Verwendung der erfindungsgemäßen Formmassen in der Extrusion, bevorzugt im Extrusionsprozess oder in der Profil-Extrusion, im Spritzguss oder im Blasformen zur Herstellung von Erzeugnissen, bevorzugt von Formteilen oder Halbzeugen.
Gegenstand ist aber auch die Verwendung mindestens eines Polyols mit mindestens zwei und maximal 12 Hydroxylgruppen pro Molekül und einem mittleren Molekulargewicht im Bereich von 64 bis 2000 g/mol in Kombination mit mindestens einem Copolymerisat aus mindestens einem Olefin mit mindestens einem Methacrylsäurester oder Acrylsäureester eines aliphatischen Alkohols mit einem Melt-Flow-Index (MFI) gemessen bei 190°C und einer Belastung von 2,16 kg im Bereich von 100 g / 10 min bis 800 g / 10 min zur Reduktion oder Verhinderung thermooxidativer Schädigungen an Polyamid basierten Formmassen oder aus diesen Formmassen herzustellenden Polyamid basierten Erzeugnissen.The present application also relates to the use of the molding compositions according to the invention in extrusion, preferably in the extrusion process or in profile extrusion, in injection molding or in blow molding for the production of products, preferably of molded parts or semi-finished products.
However, the subject matter is also the use of at least one polyol having at least two and at most 12 hydroxyl groups per molecule and an average molecular weight in the range from 64 to 2000 g / mol in combination with at least one copolymer of at least one olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol with a melt flow index (MFI) measured at 190 ° C and a load of 2.16 kg in the range of 100 g / 10 min to 800 g / 10 min for reducing or preventing thermo-oxidative damage to or from polyamide-based molding compositions Molded polyamide based products.

BeispieleExamples

Die einzelnen Komponenten der erfindungsgemäßen thermoplastischen Formmassen sowie der Komponenten der Vergleichsbeispiele wurden in einem Zweiwellenextruder des Typs ZSK 26 Compounder der Firma Coperion Werner & Pfleiderer (Stuttgart, Deutschland) bei einer Temperatur von ca. 280 °C gemischt, als Strang in ein Wasserbad ausgetragen, bis zur Granulierfähigkeit abgekühlt und granuliert. Das Granulat wurde bei 70°C im Vakuumtrockenschrank bis zur Gewichtskonstanz getrocknet.
Anschließend wurde das Granulat auf einer Spritzgieß-Maschine vom Typ Arburg SG370-173732 bei Massetemperaturen im Bereich von 270 bis 300°C und Werkzeugtemperaturen im Bereich von 80 bis 100°C zu Schulterstäben (4mm Dicke gem. ISO 528) und Platten mit den Maßen 400 • 250 • 1,5 mm3 (Bsp. 1 und Vgl.-Bsp. 1) sowie zu Platten mit den Maßen 60 • 4 • 4 mm3 (Bsp. 2 und Vgl.-Bsp. 2 und 3) verarbeitet.
Die mechanischen Eigenschaften der aus den erfindungsgemäßen Zusammensetzungen in Beispiel 2 und aus den Zusammensetzungen für die Vergleichsbeispiele 2 und 3 hergestellten Erzeugnisse wurden im Zugversuch nach ISO 527 bestimmt. Die Stabilität gegen thermooxidative Schädigung wird durch Lagerung der Probekörper bei 200 °C für 1008 h mit anschließendem Zugversuch geprüft.The individual components of the thermoplastic molding compositions according to the invention and the components of the comparative examples were mixed in a twin-screw extruder of the ZSK 26 compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany) at a temperature of about 280 ° C., discharged as a strand into a water bath, cooled to Granulierfähigkeit and granulated. The granules were dried at 70 ° C in a vacuum oven to constant weight.
Subsequently, the granules were molded on an injection molding machine of the type Arburg SG370-173732 at melt temperatures in the range of 270 to 300 ° C and mold temperatures in the range of 80 to 100 ° C to shoulder bars (4mm thickness according to ISO 528) and plates with the dimensions 400 • 250 • 1.5 mm 3 (example 1 and comp. Example 1) as well as plates with the dimensions 60 • 4 • 4 mm 3 (example 2 and comp. Examples 2 and 3).
The mechanical properties of the products prepared from the inventive compositions in Example 2 and from the compositions for Comparative Examples 2 and 3 were determined in a tensile test according to ISO 527. The stability against thermooxidative damage is tested by storage of the specimens at 200 ° C for 1008 h followed by tensile testing.

Die Viskosität der thermoplastischen Formmassen in Beispiel 1 (nicht erfindungsgemäßes Beispiel) und die Viskosität der Formmasse für das Vergleichsbeispiel 1 im geschmolzenen Zustand wurde mit einem Kapillar-Viskosimeter gemäß ISO 11443 bei einer Temperatur von 290 °C bestimmt.
Die Viskosität der thermoplastischen Formmassen in Beispiel 2 und Vergleichsbeispiel 2 und 3 im geschmolzenen Zustand wurde als Volumenfließindex gemäß DIN EN ISO 1133-1 bei einer Temperatur von 290 °C mit einer Vorheizzeit von 10 min und einem Belastungsgewicht von 5kg bestimmt.The viscosity of the thermoplastic molding compositions in Example 1 (not according to the invention) and the viscosity of the molding composition for Comparative Example 1 in the molten state was determined using a capillary viscometer according to ISO 11443 at a temperature of 290 ° C.
The viscosity of the thermoplastic molding compositions in Example 2 and Comparative Examples 2 and 3 in the molten state was determined as a volume flow index according to DIN EN ISO 1133-1 at a temperature of 290 ° C with a preheating time of 10 minutes and a load weight of 5 kg.

Platten in Beispiel 1 (nicht erfindungsgemäß) und Vergleichsbeispiel 1 wurden zwei unterschiedlichen feuchten Klimabedingungen ausgesetzt. Die Platten wurden für 48h bei 90 % relativer Feuchte (r.F.) und 85 °C sowie für 168 h bei 90 % r.F. und 40 °C gelagert. Die Platten in Beispiel 2 und Vergleichsbeispiel 2 und 3 wurden für bis zu 672 h bei 85 % r.F und 85 °C gelagert. Die Belagsbildung nach der Lagerung wurde mit einem Belagindex zwischen 1 und 6 bewertet. Dabei bedeutet ein Belagindex von 1, dass kein Belag gebildet wurde. Ein Belagindex von 3 steht für einen deutlich sichtbaren aber dünnen Belag. Ein Belagindex von 6 bedeutet eine massive Belagsbildung über die gesamte Platte.Plates in Example 1 (not according to the invention) and Comparative Example 1 were exposed to two different humid climatic conditions. The plates were stored for 48 h at 90% relative humidity (RH) and 85 ° C and for 168 h at 90% RH and 40 ° C. The plates in Example 2 and Comparative Examples 2 and 3 were stored for up to 672 hours at 85% RH and 85 ° C. The deposit formation after storage was rated with a coating index between 1 and 6. In this case, a coating index of 1 means that no coating has been formed. A covering index of 3 stands for a clearly visible but thin surface. A covering index of 6 means a massive deposit formation over the whole plate.

Die in den folgenden Tabellen 1 und 2 dargestellten Zusammensetzungen wurden alle nach der oben beschriebenen Weise verarbeitet und geprüft.The compositions shown in Tables 1 and 2 below were all processed and tested as described above.

Verwendete Materialien: Materials used :

  • Polyamid 6.6, z. B. Vydyne® 50 BWFS von Ascend Performance Materials LLCPolyamide 6.6, z. B. Vydyne® 50 BWFS from Ascend Performance Materials LLC
  • Polyamid 6, linear mit einer Viskositätszahl bestimmt in einer 0,5 gew.-%igen Lösung in 96 gew.-%iger Schwefelsäure bei 25 °C gemäß ISO 307 von 145 ml/gPolyamide 6, linear with a viscosity number determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307 of 145 ml / g
  • Glasfaser, z. B. CS7928 von Lanxess Deutschland GmbHFiberglass, z. CS7928 from Lanxess Deutschland GmbH
  • Montanwachsester, z. B. Licowax® E von Clariant GmbH [ CAS No. 73138-45-1 ]Montan wax ester, z. B. Licowax® E from Clariant GmbH CAS No. 73138-45-1 ]
  • Kupfer(I)-Iodid [ CAS No. 7681-65-4 ], d99 < 70 µmCopper (I) iodide [ CAS No. 7681-65-4 ], d99 <70 μm
  • Kaliumbromid [ CAS No. 7758-02-3 ], d99 < 70 µmPotassium bromide [ CAS No. 7758-02-3 ], d99 <70 μm
  • Talkum [ CAS No. 14807-96-6 ]Talcum [ CAS No. 14807-96-6 ]
  • Organischer Stabilisator, z. B. Irganox® 1098 [ CAS No. 23128-74-7 ] von BASF SE, N,N'-Hexamethylene bis[3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionamide]Organic stabilizer, e.g. Irganox® 1098 [ CAS No. 23128-74-7 ] from BASF SE, N, N'-hexamethylenes to [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamides]
  • Schlagzähigkeitsmodifikator, z. B. Tafmer® MH7020 von Mitsui Chemicals, Inc., ein säuremodifiziertes Polyolefin [ CAS No. 63625-36-5 ].Impact modifier, e.g. Tafmer® MH7020 from Mitsui Chemicals, Inc., an acid-modified polyolefin [ CAS No. 63625-36-5 ].
  • Dipentaerythrit, [ CAS-No. 126-58-9 ], z.B. Di-Penta 93 der Perstorp Service GmbHDipentaerythritol, CAS-No. 126-58-9 ], eg Di-Penta 93 from Perstorp Service GmbH
  • Copolymerisat aus Ethen und 2-Ethylhexylacrylat, z. B. Lotryl® 37 EH 550 [ CAS-No. 26984-27-0 ] von Arkema GmbHCopolymer of ethene and 2-ethylhexyl acrylate, z. Lotryl® 37 EH 550 [ CAS-No. 26984-27-0 ] by Arkema GmbH
Tabelle 1Table 1 Vgl.-Bsp. 1Comp. 1 Bsp. 1Example 1 Polyamid 6.6Polyamide 6.6 38,2338.23 36,7336.73 Glasfaserglass fiber 60,0060,00 60,0060,00 MontanwachsesterMontan wax Sester 0,090.09 0,090.09 Kupfer(I)-IodidCopper (I) iodide 0,020.02 0,020.02 Kalium-BromidPotassium bromide 0,060.06 0,060.06 Dipentaerythritdipentaerythritol 1,351.35 1,351.35 Copolymerisat aus Ethen und 2-EthylhexylacrylatCopolymer of ethene and 2-ethylhexyl acrylate 1,501.50 Rußsoot 0,150.15 0,150.15 Nigrosinnigrosine 0,100.10 0,100.10 Schmelzeviskosität bei 270 °C/1000 1/s [Pa s]Melt viscosity at 270 ° C / 1000 1 / s [Pa s] 180180 181181 Schmelzeviskosität bei 270 °C/1500 1/s [Pa s]Melt viscosity at 270 ° C / 1500 1 / s [Pa s] 154154 148148 Schmelzeviskosität bei 290 °C/1000 1/s [Pa s]Melt viscosity at 290 ° C / 1000 1 / s [Pa s] 8282 7979 Schmelzeviskosität bei 290 °C/1500 1/s [Pa s]Melt viscosity at 290 ° C / 1500 1 / s [Pa s] 7171 6969 Belagindex nach 24h bei 85 °C/90% r.F.Coating index after 24h at 85 ° C / 90% r.F. 2,52.5 1,01.0 Belagindex nach 168h bei 40 °C/90% r.F.Coating index after 168h at 40 ° C / 90% r.F. 2,52.5 1,01.0 Tabelle 2Table 2 Vgl.-Bsp. 2Comp. 2 Vgl.-Bsp. 3Comp. 3 Bsp. 2Ex. 2 Polyamid 6Polyamide 6 67,3267.32 65,3265.32 63,3263.32 Glasfaserglass fiber 30,0030.00 30,0030.00 30,0030.00 MontanwachsesterMontan wax Sester 0,160.16 0,160.16 0,160.16 Talkumtalc 0,020.02 0,020.02 0,020.02 organischer Stabilisatororganic stabilizer 0,500.50 0,500.50 0,500.50 Schlagzähigkeitsmodifikatorimpact modifier 2,002.00 2,002.00 2,002.00 Dipentaerythritdipentaerythritol 2,002.00 2,002.00 Copolymerisat aus Ethen und 2-EthylhexylacrylatCopolymer of ethene and 2-ethylhexyl acrylate 2,002.00 Volumenfließindex bei 290 °C / 5 kg [cm3/10 min]Volume-flow index at 290 ° C / 5kg [cm 3/10 min] 6969 217217 241241 Belagindex nach 168h bei 85 °C/85% r.F.Coating index after 168h at 85 ° C / 85% r.F. 1,01.0 1,51.5 1,01.0 Belagindex nach 672h bei 85 °C/85% r.F.Coating index after 672h at 85 ° C / 85% r.F. 1,01.0 2,02.0 1,01.0 Bruchspannung nach 0 h bei 200 °C [MPa]Breaking stress after 0 h at 200 ° C [MPa] 176176 167167 154154 Bruchspannung nach 1008 h bei 200 °C [MPa]Breaking stress after 1008 h at 200 ° C [MPa] 151151 183183 171171 relative Veränderung der Bruchspannung [%]relative change in breaking stress [%] -14-14 +10+10 +11+11

In Tabelle 1 zeigen die thermoplastischen Formmassen des Vergleichsbeispiels 1 eine deutliche Belagsbildung unter beiden geprüften Klimabedingungen. Durch die Zugabe des Copolymerisats aus Ethen und 2-Ethylhexylacrylat wird diese Belagsbildung deutlich reduziert. Nach Lagerung unter beiden Klimabedingungen wird keine Belagsbildung mehr beobachtet. Die Viskosität der Formmasse wird durch Zugabe des Copolymerisats nicht erhöht. Daraus kann geschlossen werden, dass die fließverbessernde Wirkung des Dipentaerythrit durch die Zugabe des Copolymerisats nicht reduziert wird.In Table 1, the thermoplastic molding compositions of Comparative Example 1 show a clear deposit formation under both tested climatic conditions. The addition of the copolymer of ethene and 2-ethylhexyl acrylate significantly reduces this deposit formation. After storage under both climatic conditions no deposit formation is observed. The viscosity of the molding composition is not increased by adding the copolymer. From this it can be concluded that the flow-improving effect of dipentaerythritol is not reduced by the addition of the copolymer.

In Tabelle 2 zeigt der Vergleich der Ergebnisse für den Volumenfließindex von Vergleichsbeispiel 3 und Beispiel 2, dass auch bei diesen Formmassen die Zugabe des Copolymerisats die viskositätsreduzierende Wirkung des Dipentaerythrit nicht beeinträchtigt. Der positive Effekt des Dipentaerythrits ist beim Vergleich der Ergebnisse des Volumenfließindex von Vergleichsbeispiel 2 und 3 ersichtlich.In Table 2, the comparison of the results for the volume flow index of Comparative Example 3 and Example 2 shows that even with these molding compositions, the addition of the copolymer does not impair the viscosity-reducing effect of dipentaerythritol. The positive effect of dipentaerythritol can be seen by comparing the results of the volumetric flow index of Comparative Examples 2 and 3.

Die Ergebnisse für den Belagbildungsindex nach Lagerung bei 85 °C / 85 % r.F. zeigen, dass die Zugabe von Dipentaerythrit zu einer deutlichen Steigerung der Belagsbildung führt (Vgl.-Bsp. 2 und 3). Dieser Effekt kann durch die zusätzliche Zugabe des Copolymerisats in Beispiel 2 vermieden werden. Es wird in diesem Beispiel keine Belagsbildung mehr beobachtet.The results for the pad formation index after storage at 85 ° C / 85% r.F. show that the addition of dipentaerythritol leads to a significant increase in deposit formation (cf. Examples 2 and 3). This effect can be avoided by the additional addition of the copolymer in Example 2. No deposit formation is observed in this example.

Bei der Formmasse mit herkömmlichem Kupferstabilisator (Vgl.-Bsp. 2) führt die Lagerung über 1008 h bei 200 °C zu einer 14%igen Reduktion der Bruchspannung im Zugversuch. Die stabilisierende Wirkung des Dipentaerythrit führt dazu, dass die Bruchspannung nach 1008 h Lagerung bei 200 °C um 10 % zunimmt (Vgl.-Bsp. 3). Diese stabilisierende Wirkung wird durch die Zugabe des Copolymerisats in Beispiel 2 nicht negativ beeinflusst. In Beispiel 2 steigt die Bruchspannung um 11 % nach 1008 h Lagerung bei 200 °C.In the case of the molding composition with conventional copper stabilizer (Comp. Ex. 2), storage at 200 ° C. for 1008 h leads to a 14% reduction in the tensile stress at break. The stabilizing effect of dipentaerythritol causes the fracture stress to increase by 10% after 1008 hours of storage at 200 ° C. (Comp. Ex. 3). This stabilizing effect is not adversely affected by the addition of the copolymer in Example 2. In Example 2, the breaking stress increases by 11% after 1008 hours of storage at 200 ° C.

Claims (16)

  1. Thermoplastic moulding compositions comprising
    (a) 10% to 99.8% by weight of at least one polyamide,
    (b) 0.1% to 10% by weight of at least one polyol having at least two and not more than 12 hydroxyl groups per molecule and a mean relative molecular mass in the range from 64 to 2000 g/mol and
    (c) 0.1% to 10% by weight of at least one copolymer of at least one olefin with at least one methacrylate or acrylate of an aliphatic alcohol which has a melt flow index (MFI) measured at 190°C with a load of 2.16 kg in the range from 100 g/10 min to 800 g/10 min, the content of the olefin in the copolymer (c) being in the range from 50% to 90% by weight and the content of the acrylates or methacrylates in the copolymer for use as component (c) being in the range from 10% to 50% by weight with the proviso that the sum total of all the percentages by weight is always 100 and, in the case of use of polyols (b) which are mixtures of oligomeric and/or polymeric polyols, it is the number-average molecular weight (Mn) rather than the relative molecular mass that determines the limit of the range for that part of the mixture, where the proportion of components (a), (b) and (c) is in the range from 50% to 100% by weight and where the further components or other constituents are additives selected by the person skilled in the art in accordance with the later use of the products.
  2. Thermoplastic moulding compositions according to Claim 1, characterized in that they comprise, in addition to components (a) to (c), also d) 5% to 80% by weight of at least one filler or reinforcer, preferably glass fibres or carbon fibres, where the proportions of components (a) to (c) are reduced such that the sum total of all the percentages by weight is always 100.
  3. Thermoplastic moulding compositions according to Claim 1 or 2, characterized in that they comprise, in addition to components (a) to (d) or instead of (d), also (e) 0.1% to 20% by weight of at least one form of carbon black and/or nigrosin, where the proportions of components (a) to (c) and any (d) are reduced such that the sum total of all the percentages by weight is always 100.
  4. Thermoplastic moulding compositions according to any of Claims 1 to 3, characterized in that amorphous polyamides, semicrystalline polyamides or partly crystalline polyamides are used.
  5. Thermoplastic moulding compositions according to Claim 4, characterized in that a partly crystalline polyamide having a viscosity number determined in a 0.5% by weight solution in 96% by weight sulphuric acid at 25°C to ISO 307 in the range from 80 to 180 ml/g is used.
  6. Thermoplastic moulding compositions according to Claim 5, characterized in that aliphatic or semiaromatic polyamides are used.
  7. Thermoplastic moulding compositions according to any of Claims 1 to 6, characterized in that at least one polyol from the group of pentaerythritol, dipentaerythritol and tripentaerythritol is used as component (b).
  8. Thermoplastic moulding compositions according to any of Claims 1 to 7, characterized in that the copolymer (c) consists to an extent of less than 4% by weight of monomer units containing further reactive functional groups.
  9. Thermoplastic moulding compositions according to Claim 8, characterized in that the olefin is copolymerized with 2-ethylhexyl acrylate in the copolymer (c).
  10. Thermoplastic moulding compositions according to Claim 8 or 9, characterized in that the olefin in the copolymer (c) is ethene.
  11. Thermoplastic moulding compositions according to any of Claims 1 to 10, characterized in that the mass ratio between component (b) and component (c) is between 5:1 and 1:5.
  12. Process for producing products, characterized in that the thermoplastic moulding compositions according to any of Claims 1 to 11 are mixed in the proportions by weight specified and these are subjected to an injection moulding, extrusion or blow moulding operation.
  13. Products obtainable by injection moulding, extrusion or blow moulding of thermoplastic moulding compositions according to any of Claims 1 to 11.
  14. Products according to Claim 13, characterized in that they are fibres, films, semifinished products or mouldings.
  15. Use of at least one polyol having at least two and not more than 12 hydroxyl groups per molecule and a mean relative molecular mass in the range from 64 to 2000 g/mol in combination with at least one copolymer of at least one olefin with at least one methacrylate or acrylate of an aliphatic alcohol having a melt flow index (MFI) measured at 190°C and a load of 2.16 kg in the range from 100 g/10 min to 800 g/10 min for reduction or prevention of thermooxidative damage to polyamide-based moulding compositions or polyamide-based products that can be produced from these moulding compositions, where the number-average molecular weight (Mn) replaces the relative molecular mass for that part of the mixture in the case of use of polyols that are mixtures of oligomeric and/or polymeric polyols.
  16. Use according to Claim 15, characterized in that the products are articles for the electrical, electronics, telecommunications, information technology, solar and computer industries, for the household, for sport, for medical applications or for the entertainment industry.
EP14194508.9A 2013-12-05 2014-11-24 Polyamide compositions Active EP2881439B1 (en)

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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2910597B1 (en) * 2014-02-21 2018-12-26 LANXESS Deutschland GmbH Thermoplastic compositions
KR101602814B1 (en) * 2015-08-24 2016-03-22 (주)디티알 Polyamide 66 resin composition reinforced with glass fiber for high tensile strength and manufacturing method thereof
CN105949752A (en) * 2016-05-11 2016-09-21 南京京锦元科技实业有限公司 Glass fiber reinforced polyamide resin composite
WO2018031564A1 (en) 2016-08-08 2018-02-15 Ticona Llc Thermally conductive polymer composition for a heat sink
KR101884873B1 (en) * 2017-10-12 2018-08-02 충남대학교산학협력단 Fibers having a functional group and methods for their preparation
KR102043301B1 (en) * 2018-03-28 2019-11-12 (주)우성케미칼 Polyamide resin composition and product prepared therefrom
KR102054332B1 (en) * 2018-06-26 2019-12-10 엘에스산전 주식회사 Arc Extinguish Chamber Base of Molded Case Circuit Breaker
CN109021559A (en) * 2018-07-18 2018-12-18 辽宁丰迪发动机进气***有限公司 A kind of dedicated PA6 composite material of motor intake manifold
KR102452073B1 (en) * 2018-12-12 2022-10-06 주식회사 엘지화학 Glass fiber reinforced polyamide resin composition, method for preparing thereof and molding product comprising the same
JP7303004B2 (en) * 2019-03-29 2023-07-04 三井化学株式会社 Polyamide resin composition and molded article
EP3848410A1 (en) 2020-01-09 2021-07-14 L. Brüggemann GmbH & Co. KG Polyamide materials with improved long-term properties
WO2021151850A1 (en) 2020-01-27 2021-08-05 Basf Se Thermoplastic polyamide molding compositions that resist heat
CN113121992B (en) * 2021-04-06 2022-07-12 万华化学（宁波）有限公司 Halogen-free flame-retardant solvent-resistant PA12 material and preparation method thereof
CN116355402A (en) * 2021-12-28 2023-06-30 金发科技股份有限公司 Polyamide molding composition and preparation method and application thereof

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2512606A (en) 1945-09-12 1950-06-27 Du Pont Polyamides and method for obtaining same
US2494563A (en) 1947-01-08 1950-01-17 Du Pont Bis (4-aminocyclohexyl) methane
US2516585A (en) 1948-12-21 1950-07-25 Du Pont Synthetic linear polyamides containing intralinear cyclic groups and process for obtaining same
US2696482A (en) 1951-07-19 1954-12-07 Du Pont Transparent synthetic linear polyamide and process for producing same
IL24111A (en) 1964-08-24 1969-02-27 Du Pont Linear polyamides
DE1595354C3 (en) 1966-10-18 1978-12-07 Basf Ag Process for the production of polyamides
NL137599C (en) 1968-07-02
BE792063A (en) 1971-12-02 1973-05-29 Bayer Ag TRANSPARENT COPOLYAMIDES
US3842045A (en) 1972-07-05 1974-10-15 Phillips Petroleum Co Amorphous polyamides from bis(4-aminocyclohexyl)methane and a mixture of straight chain dicarboxylic acids
DE2405985A1 (en) 1974-02-08 1975-08-21 Hoechst Ag Thermoplastic amorphous polyamide mould compsns - rendered non-combustible by incorporating red phosphorus
CH624970A5 (en) 1975-09-22 1981-08-31 Inventa Ag Process for the preparation of glass-transparent polyamide
GB1550051A (en) 1976-07-22 1979-08-08 Bayer Ag Tetraalkylated biscyclohexylamine derivatives
DE2855928A1 (en) 1978-12-23 1980-07-10 Bayer Ag NEW COPOLYAMID
DE2936759A1 (en) 1979-09-12 1981-04-02 Chemische Werke Hüls AG, 4370 Marl TRANSPARENT COPOLYAMID
JP4284808B2 (en) 1999-03-30 2009-06-24 宇部興産株式会社 Injection welding material
DE102004027872A1 (en) * 2004-06-08 2006-01-05 Lanxess Deutschland Gmbh Thermoplastic molding compound used in thin-wall technology, especially extrusion, injection and multi-injection molding, contains thermoplastic polyamide and olefin-alkyl (meth)acrylate copolymer
JP4620734B2 (en) * 2004-06-08 2011-01-26 ランクセス・ドイチュランド・ゲーエムベーハー Polyamide molding composition with improved flow properties
EP1937766A4 (en) 2005-09-29 2012-07-11 Nilit Ltd Modified polyamides, uses thereof and process for their preparation
DE102005050958A1 (en) * 2005-10-25 2007-04-26 Lanxess Deutschland Gmbh Polyamide molding composition for use in thin walled applications such as vehicular coolant or oil circuits has its viscosity reduced by addition of an olefin/(meth)acrylic ester copolymer
ATE423804T1 (en) 2006-11-14 2009-03-15 Bond Laminates Gmbh FIBER COMPOSITE MATERIAL AND METHOD FOR THE PRODUCTION THEREOF
EP2307480B1 (en) 2008-07-30 2016-08-17 E. I. du Pont de Nemours and Company Heat resistant thermoplastic articles including co-stabilizers
DE102008046682A1 (en) 2008-09-10 2010-03-11 Basf Se Thermoplastic molded mass, useful to produce molded body, fiber and film, comprises polyamide made of units derived from dicarboxylic acids and cycloaliphatic diamines, and units derived from further polyamide-forming monomer and additives
US20110028628A1 (en) 2009-07-30 2011-02-03 E.I. Du Pont De Nemours And Company Heat resistant polyamide compositions having high amine ends
CN102030982B (en) 2009-09-29 2013-03-13 E.I.内穆尔杜邦公司 Polymer composition containing polyol and co-stabilizer
EP2481775A1 (en) * 2011-01-28 2012-08-01 LANXESS Deutschland GmbH Use of moulding materials
EP2562219B1 (en) * 2011-08-25 2016-12-21 LANXESS Deutschland GmbH Thermoplastic moulded substances with increased hydrolysis resistance
DE102011084519A1 (en) 2011-10-14 2013-04-18 Evonik Industries Ag Use of a multilayer film for the production of photovoltaic modules

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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